analytical 
 and preparative thin layer chromatography was carried out on silica 
 gel 60 f-254 plates . products were visualized using uv or by staining 
 with 5% aqueous sulfuric acid or ceric ammonium molybdate . nmr spectra 
 were recorded on a nmr spectrometer at 500 mhz for h nmr 
 and 125 mhz for c nmr . chemical shifts are reported in 
 ppm relative to tms ( for h nmr in cdcl3 ) or 
 cdcl3 ( for c nmr in cdcl3 ) . for h nmr spectra , data are reported as follows :  shift , 
 multiplicity ( s = singlet , m = multiplet , t = triplet , d = doublet , 
 dd = doublet of doublets , td = triplet of doublets , q = quartet , brs 
 = broad singlet ) , coupling constants are reported in hz . low - resolution 
 mass spectra ( lrms ) were recorded using a esi - ms with an additional 
 apci source . high - resolution mass spectra ( hrms ) were obtained on 
 fourier transform ion cyclotron resonance mass spectrometer ( ft - icr - ms ) 
 with direct analysis in real time ( dart ) ionization source . optical 
 rotations were measured at 589 nm in a 5 cm cell at 24 c . all other chemicals 
 were purchased at the highest possible quality and used as received . compounds 4,6,8,10,15,20,23,27 , and 30(25 ) were prepared according to literature methods to 
 a solution of 1 ( 0.59 mmol ) and -pinene 
 ( 2.0 mmol ) in dcm ( 58 ml ) and h2o ( 2.9 ml ) , was added ddq 
 ( 1.1 mmol ) . the reaction was stirred at room temperature under argon 
 for 4 h and monitored by tlc . the reaction mixture was then diluted 
 with dcm ( 50 ml ) , and the organic layer was washed 3 times with 50 
 ml of 2 m naoh . the residue 
 was purified by flash chromatography on silica gel ( 30% ethyl acetate 
 in hexanes ) to afford 2 ( 323 mg , 96% ) as a white powder . to a solution of 1 ( 0.59 mmol ) in dcm ( 59 ml ) and 
 h2o ( 2.9 ml ) , the reaction was 
 stirred at room temperature under argon for 4 h and monitored by tlc . the reaction mixture was then diluted with dcm ( 75 ml ) , and the organic 
 layer was washed 3 times with 50 ml of 2 m naoh . the residue was purified by flash chromatography on 
 silica gel ( 30% ethyl acetate in hexanes ) to afford 2 ( 183 mg , 54% ) as a white powder . mp : 151152 
 c ; [  ] d = 30.0 ( c 1.05 , ch2cl2 ) ; h nmr 
 ( 500 mhz , cdcl3 )  7.417.26 ( m , 10h ) , 6.976.91 
 ( m , 2h ) , 6.846.78 ( m , 2h ) , 4.95 ( dd , j = 
 9.9 , 2.0 hz , 1h ) , 4.824.64 ( m , 5h ) , 3.76 ( s , 3h ) , 3.713.56 
 ( m , 1h ) , 3.503.40 ( m , 1h ) , 3.393.25 ( m , 2h ) , 2.99 
 ( t , j = 8.9 hz , 1h ) , 2.45 ( ddd , j = 11.4 , 6.3 , 1.7 hz , 1h ) , 2.26 ( ddd , j = 13.7 , 
 6.8 , 1.7 hz , 1h ) , 2.08 ( d , j = 3.2 hz , 1h ) , 1.88 
 ( td , j = 12.1 , 10.1 hz , 1h ) , 1.60 ( td , j = 12.0 , 9.8 hz , 1h ) , 1.35 ( t , j = 6.5 hz , 6h ) ; c nmr ( 125 mhz , cdcl3 )  155.0 , 151.2 , 138.7 , 
 138.2 , 128.7 , 128.4 , 128.1 , 127.9 , 127.6 , 127.5 , 117.9 , 114.5 , 100.5 , 
 98.5 , 85.8 , 82.5 , 77.6 , 75.2 , 71.9 , 71.6 , 71.3 , 71.0 , 55.6 , 39.3 , 
 37.0 , 18.5 , 18.4 ; lrms ( esi ) m / z : [ m+na ] calcd for c33h40o8na 587.26 ; found 587.45 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c33h44no8 582.3061 ; found 582.3058 . the title compound was prepared according 
 to procedure a using 3 ( 250 mg , 0.48 mmol ) and -pinene 
 ( 0.24 ml , 11.6 mmol ) dissolved in dcm ( 48 ml ) and h2o ( 22.4 
 ml ) , the solution was then treated with ddq ( 220 mg , 0.97 mmol ) for 
 4 h. the title compound was purified by flash column chromatography 
 on silica gel ( 20% ethyl acetate in hexanes ) to afford compound 4 ( 159 mg , 89% ) as a white solid . the spectroscopic data is 
 in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 )  7.527.46 
 ( m , 2h ) , 7.437.27 ( m , 8h ) , 5.58 ( s , 1h ) , 4.97 ( d , j = 11.6 hz , 1h ) , 4.82 ( d , j = 3.8 hz , 
 1h ) , 4.79 ( d , j = 11.6 hz , 1h ) , 4.30 ( dd , j = 10.0 , 4.6 hz , 1h ) , 3.893.80 ( m , 2h ) , 3.803.70 
 ( m , 2h ) , 3.65 ( t , j = 9.2 hz , 1h ) , 3.46 ( s , 3h ) , 
 2.29 ( d , j = 7.4 hz , 1h ) . the title compound was prepared according 
 to procedure b using 3 ( 250 mg , 0.48 mmol ) in dcm ( 48 
 ml ) and h2o ( 2.4 ml ) , ddq ( 220 mg , 0.97 mmol ) was then 
 added . the title compound was purified by flash column chromatography 
 on silica gel ( 20% ethyl acetate in hexanes ) to afford compound 4 ( 158 mg , 89% ) . the title compound was prepared according 
 to procedure a using 5 ( 234 mg , 0.45 mmol ) and -pinene 
 ( 0.24 ml , 1.5 mmol ) dissolved in dcm ( 46 ml ) and h2o ( 2.3 
 ml ) , the solution was then treated with ddq ( 206 mg , 0.9 mmol ) for 
 4 h. the title compound was purified by flash column chromatography 
 on silica gel ( 20% ethyl acetate in hexanes ) to afford compound 6 ( 155 mg , 93% ) as a white solid . the spectroscopic data is 
 in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 )  7.527.44 
 ( m , 2h ) , 7.427.28 ( m , 8h ) , 5.52 ( s , 1h ) , 4.79 ( d , j = 12.2 hz , 1h ) , 4.71 ( d , j = 12.2 hz , 
 1h ) , 4.61 ( d , j = 3.6 hz , 1h ) , 4.26 ( dd , j = 10.2 , 4.8 hz , 1h ) , 4.15 ( td , j = 9.3 , 
 2.2 hz , 1h ) , 3.81 ( td , j = 10.0 , 4.8 hz , 1h ) , 3.70 
 ( t , j = 10.3 hz , 1h ) , 3.533.43 ( m , 2h ) , 3.38 
 ( s , 3h ) , 2.55 ( d , j = 2.2 hz , 1h ) . the title compound was prepared according 
 to procedure a using 7 ( 100 mg , 0.19 mmol ) and -pinene 
 ( 0.10 ml , 0.64 mmol ) dissolved in dcm ( 19 ml ) and h2o ( 0.95 
 ml ) , the solution was then treated with ddq ( 86 mg , 0.38 mmol ) for 
 4 h. the title compound was purified by flash column chromatography 
 on silica gel ( 40% ethyl acetate in hexanes ) to afford compound 8 ( 63 mg , 86% ) as a white solid . the spectroscopic data is 
 in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 )  7.527.46 
 ( m , 2h ) , 7.447.26 ( m , 8h ) , 5.58 ( s , 1h ) , 4.98 ( d , j = 11.6 hz , 1h ) , 4.79 ( d , j = 11.6 hz , 
 1h ) , 4.404.31 ( m , 2h ) , 3.81 ( t , j = 10.3 
 hz , 1h ) , 3.753.63 ( m , 2h ) , 3.58 ( s , 3h ) , 3.573.52 
 ( m , 1h ) , 3.46 ( ddd , j = 10.1 , 8.8 , 5.0 hz , 1h ) , 2.43 
 ( d , j = 2.2 hz , 1h ) . the title compound was prepared according 
 to procedure b using 7 ( 100 mg , 0.19 mmol ) dissolved 
 in dcm ( 19 ml ) and h2o ( 0.95 ml ) , the solution was then 
 treated with ddq ( 86 mg , 0.38 mmol ) for 3 h. the title compound was 
 purified by flash column chromatography on silica gel ( 40% ethyl acetate 
 in hexanes ) to afford compound 20 ( 62 mg , 85% ) as a white 
 solid . the spectroscopic data is in good agreement with previously 
 reported data.h nmr ( 500 
 mhz , cdcl3 )  7.527.46 ( m , 2h ) , 7.447.26 
 ( m , 8h ) , 5.58 ( s , 1h ) , 4.98 ( d , j = 11.6 hz , 1h ) , 
 4.79 ( d , j = 11.6 hz , 1h ) , 4.404.31 ( m , 2h ) , 
 3.81 ( t , j = 10.3 hz , 1h ) , 3.753.63 ( m , 2h ) , 
 3.58 ( s , 3h ) , 3.573.52 ( m , 1h ) , 3.46 ( ddd , j = 10.1 , 8.8 , 5.0 hz , 1h ) , 2.43 ( d , j = 2.2 hz , 
 1h ) . the title compound was prepared according 
 to procedure a using 9 ( 100 mg , 0.19 mmol ) and -pinene 
 ( 0.10 ml , 0.64 mmol ) dissolved in dcm ( 19 ml ) and h2o ( 0.95 
 ml ) , the solution was then treated with ddq ( 86 mg , 0.38 mmol ) for 
 4 h. the title compound was purified by flash column chromatography 
 on silica gel ( 40% ethyl acetate in hexanes ) to afford compound 10 ( 69 mg , 94% ) as colorless oil . the spectroscopic data is 
 in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 )  7.527.46 
 ( m , 2h ) , 7.427.25 ( m , 8h ) , 5.61 ( s , 1h ) , 4.84 ( d , j = 11.8 hz , 1h ) , 4.764.67 ( m , 2h ) , 4.27 ( dd , j = 9.7 , 4.3 hz , 1h ) , 4.10 ( t , j = 9.3 
 hz , 1h ) , 4.043.99 ( m , 1h ) , 3.933.76 ( m , 3h ) , 3.36 
 ( s , 3h ) , 2.80 ( d , j = 1.5 hz , 1h ) . the title compound was prepared according 
 to procedure b using 9 ( 100 mg , 0.19 mmol ) dissolved 
 in dcm ( 19 ml ) and h2o ( 0.95 ml ) , the solution was then 
 treated with ddq ( 86 mg , 0.38 mmol ) for 4 h. the title compound was 
 purified by flash column chromatography on silica gel ( 40% ethyl acetate 
 in hexanes ) to afford compound 10 ( 62 mg , 85% ) as colorless 
 oil . the spectroscopic data is in good agreement with previously reported 
 data.h nmr ( 500 mhz , cdcl3 )  7.527.46 ( m , 2h ) , 7.427.25 ( m , 8h ) , 
 5.61 ( s , 1h ) , 4.84 ( d , j = 11.8 hz , 1h ) , 4.764.67 
 ( m , 2h ) , 4.27 ( dd , j = 9.7 , 4.3 hz , 1h ) , 4.10 ( t , j = 9.3 hz , 1h ) , 4.043.99 ( m , 1h ) , 3.933.76 
 ( m , 3h ) , 3.36 ( s , 3h ) , 2.80 ( d , j = 1.5 hz , 1h ) . the title compound 
 was prepared according to procedure a using 11 ( 462.8 
 mg , 0.885 mmol ) and -pinene ( 0.47 ml , 3.03 mmol ) dissolved 
 in dcm ( 89 ml ) and h2o ( 4.4 ml ) , the solution was then 
 treated with ddq ( 400 mg , 1.77 mmol ) for 5 h. the title compound was 
 purified by flash column chromatography on silica gel ( 5% ethyl acetate 
 in toluene ) to afford compound 12 ( 251.4 mg , 74% ) as 
 a white solid . mp : 144145 c ; [  ] d = 8.4 ( c = 1.14 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) :  7.377.31 
 ( m , 5h ) , 5.02 ( t , j = 10.0 hz , 1h ) , 4.83 ( d , j = 11.7 hz , 1h ) , 4.69 ( d , j = 11.7 hz , 
 1h ) , 4.37 ( d , j = 10.0 hz , 1h ) , 3.673.63 
 ( m , 3h ) , 2.772.72 ( m , 1h ) , 2.692.62 ( m , 1h ) , 2.25 
 ( d , j = 9.5 hz , 1 h ) , 1.34 ( d , j = 6.5 hz , 3h ) , 1.25 ( t , j = 7.5 hz , 3h ) , 1.23 ( s , 
 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  178.5 , 
 138.0 , 128.6 , 128.0 , 127.9 , 82.9 , 80.1 , 76.1 , 75.0 , 74.4 , 71.1 , 38.9 , 
 27.1 , 23.6 , 17.3 , 14.9 ; lrms ( esi ) m / z : [ m+na ] calcd for c20h30o5sna 405.17 ; found 405.29 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c20h34no5s 400.2152 ; found 400.2144 . the title compound 
 was prepared according to procedure a using 13 ( 100 mg , 
 0.18 mmol ) and -pinene ( 0.09 ml , 0.60 mmol ) dissolved in dcm 
 ( 17 ml ) and h2o ( 1.9 ml ) , the solution was then treated 
 with ddq ( 79.5 mg , 0.35 mmol ) for 2 h. the title compound was purified 
 by flash column chromatography on silica gel ( 5% to 10% ethyl acetate 
 in toluene ) to afford compound 14 ( 60.7 mg , 80% ) as an 
 amorphous solid . [  ] d = + 5.5 ( c = 
 0.95 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) :  7.507.48 ( m , 2h ) , 7.347.26 ( m , 
 8h ) , 5.23 ( t , j = 9.8 hz , 1h ) , 4.664.58 ( m , 
 3h ) , 3.84 ( t , j = 2.5 hz , 1h ) , 3.623.57 ( m , 
 2h ) , 2.38 ( s , 1h ) , 1.40 ( d , j = 6.5 hz , 3h ) , 1.24 
 ( s , 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  177.0 , 
 137.4 , 133.9 , 132.2 , 128.9 , 128.7 , 128.2 , 127.8 , 127.7 , 86.9 , 80.4 , 
 74.5 , 71.9 , 69.2 , 68.6 , 38.9 , 27.3 , 16.9 ; lrms ( esi ) m / z : [ m+na ] calcd for c24h30o5sna 453.17 ; found 453.36 ; hrms ( dart ) m / z : [ m+nh4 ] calcd 
 for c24h34no5s 448.2152 ; found 448.2155 . the title compound 
 was prepared according to procedure b using 13 ( 116.7 
 mg , 0.20 mmol ) dissolved in dcm ( 20 ml ) and h2o ( 2.2 ml ) , 
 the solution was then treated with ddq ( 96.5 mg , 0.43 mmol ) for 5 
 h. the title compound was purified by flash column chromatography 
 on silica gel ( 5% to 10% ethyl acetate in toluene ) to afford compound 14 ( 73.8 mg , 84% ) as an amorphous solid . h 
 nmr ( 500 mhz , cdcl3 ) :  7.507.48 ( m , 2h ) , 
 7.347.26 ( m , 8h ) , 5.23 ( t , j = 9.5 hz , 1h ) , 
 4.664.58 ( m , 3h ) , 3.84 ( t , j = 2.5 hz , 1h ) , 
 3.623.57 ( m , 2h ) , 2.35 ( s , 1h ) , 1.40 ( d , j = 6.5 hz , 3h ) , 1.24 ( s , 9h ) . the title compound 
 was 
 prepared according to procedure a using 15(24 ) ( 60.5 mg , 0.10 mmol ) and -pinene ( 0.06 
 ml , 0.36 mmol ) dissolved in dcm ( 10.6 ml ) and h2o ( 0.53 
 ml ) , the solution was then treated with ddq ( 48 mg , 0.212 mmol ) for 
 4 h. the title compound was purified by flash column chromatography 
 on silica gel ( 5% ethyl acetate in toluene ) to afford compound 16 ( 30.9 mg , 68% ) as a white solid . the spectroscopic data 
 is in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 ) :  
 7.497.47 ( m , 2h ) , 7.387.26 ( m , 8h ) , 5.60 ( s , 1h ) , 
 5.40 ( s , 1h ) , 4.72 ( d , j = 10.9 hz , 1h ) , 4.42 ( d , j = 10.9 hz , 1h ) , 4.234.20 ( m , 1h ) , 3.72 ( dd , j = 2.4 , 9.5 hz , 1h ) , 3.62 ( t , j = 9.2 
 hz , 1h ) , 2.33 ( s , 1h ) , 1.35 ( d , j = 6.1 hz , 3h ) , 
 1.21 ( s , 9h ) . the title compound 
 was 
 prepared according to procedure b using 15(24 ) ( 115.5 mg , 0.20 mmol ) dissolved in dcm ( 20 ml ) 
 and h2o ( 2.2 ml ) , the solution was then treated with ddq 
 ( 93.3 mg , 0.41 mmol ) for 4 h. the title compound was purified by flash 
 column chromatography on silica gel ( 5% ethyl acetate in toluene ) 
 to afford compound 16 ( 61.3 mg , 70% ) as a white solid . the spectroscopic data is in good agreement with previously reported 
 data.h nmr ( 500 mhz , cdcl3 ) :  7.497.47 ( m , 2h ) , 7.377.26 ( m , 
 8h ) , 5.60 ( s , 1h ) , 5.40 ( s , 1h ) , 4.72 ( d , j = 11.1 
 hz , 1h ) , 4.42 ( d , j = 11.1 hz , 1h ) , 4.234.20 
 ( m , 1h ) , 3.72 ( dd , j = 2.4 , 9.5 hz , 1h ) , 3.62 ( t , j = 9.2 hz , 1h ) , 2.33 ( s , 1h ) , 1.35 ( d , j = 6.0 hz , 3h ) , 1.21 ( s , 9h ) . the title 
 compound was prepared according to procedure a using 17 ( 1.5 g , 3.6 mmol ) and -pinene ( 1.9 ml , 12.3 mmol ) dissolved 
 in dcm ( 360 ml ) and h2o ( 18 ml ) , the solution was then 
 treated with ddq ( 1.6 g , 7.2 mmol ) for 3 h. the title compound was 
 purified by flash column chromatography on silica gel ( 100% dichloromethane 
 then switched to 10% ethyl acetate in hexanes ) to afford compound 18 ( 1.0 g , 90% ) as a white solid . mp : 6869 c ; 
 [  ] d = 64.3 ( c = 0.97 , ch2cl2 ) ; h nmr ( 500 mhz , 
 cdcl3 )  7.427.29 ( m , 5h ) , 6.986.93 
 ( m , 2h ) , 6.856.77 ( m , 2h ) , 4.98 ( dd , j = 
 9.8 , 2.1 hz , 1h ) , 4.72 ( d , j = 11.6 hz , 1h ) , 4.51 
 ( d , j = 11.6 hz , 1h ) , 3.76 ( s , 3h ) , 3.523.37 
 ( m , 2h ) , 3.343.26 ( m , 1h ) , 2.542.47 ( m , 2h ) , 1.83 
 ( td , j = 12.0 , 9.9 hz , 1h ) , 1.38 ( d , j = 6.1 hz , 3h ) ; c nmr ( 126 mhz , cdcl3 )  
 155.2 , 151.3 , 138.0 , 128.8 , 128.1 , 127.9 , 118.0 , 117.9 , 98.6 , 78.8 , 
 75.6 , 71.9 , 71.1 , 55.8 , 36.0 , 18.1 ; lrms ( esi ) m / z : [ m+na ] calcd for c20h24o5na 367.15 ; found 367.16 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c20h28no5 362.1962 ; found 362.1947 . the title 
 compound was prepared according to procedure b using 17 ( 825 mg , 1.9 mmol ) dissolved in dcm ( 20 ml ) and h2o ( 2 
 ml ) , ddq ( 882 mg , 3.1 mmol ) was then added . the reaction was stirred 
 at room temperature under argon for 2 h and monitored by tlc . the 
 reaction mixture was diluted with dcm ( 25 ml ) , and the organic layer 
 was washed 3 times with 2 m naoh . the pooled organic layers were washed 
 with h2o , dried over na2so4 , filtered , 
 and concentrated in vacuo . the residue was purified 
 by flash column chromatography on silica gel ( 20% ethyl acetate in 
 hexanes ) to afford 18 ( 438 mg , 67% 5:1 : ) 
 as a white powder . mp : 8485 c ; [  ] d = + 98.75 ( c 1.28 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) 7.427.27 
 ( m , 5h ) , 6.98 ( d , j = 12.2 hz , 2h ) , 6.83 ( d , j = 12.2 hz , 2h ) , 5.50 ( d , j = 3.7 , 1.4 
 hz , 1h ) , 4.74 ( d , j = 11.5 hz , 1h ) , 4.57 ( d , j = 11.5 hz , 1h ) , 3.95 ( ddd , j = 11.4 , 
 8.9 , 4.8 hz , 1h ) , 3.83 ( dq , j = 9.5 , 6.2 hz , 1h ) , 
 3.77 ( s , 3h ) , 3.31 ( td , j = 9.2 , 2.1 hz , 1h ) , 2.48 
 ( dd , j = 13.0 , 4.9 , 1.5 hz , 1h ) , 2.43 ( d , j = 2.1 hz , 1h ) , 1.77 ( ddd , j = 12.9 , 11.4 , 
 3.6 hz , 1h ) , 1.26 ( d , j = 6.2 hz , 3h ) ; c nmr ( 125 mhz , cdcl3 )  154.9 , 150.8 , 138.4 , 128.7 , 
 128.0 , 127.9 , 117.9 , 114.7 , 96.8 , 77.0 , 76.2 , 71.4 , 68.4 , 55.8 , 35.1 , 
 18.0 ; lrms ( esi ) m / z : [ m+nh4 ] calcd for c20h28no5 ( m+nh4 ) 362.41 ; found 362.18 ; hrms ( dart ) m / z : [ m+nh4 ] calcd 
 for c20h28no5 362.1962 ; found 362.1971 . the 
 title compound was prepared according to procedure a using 19 ( 325 mg , 0.9 mmol ) and -pinene ( 0.8 ml , 3.6 mmol ) 
 dissolved in dcm ( 90 ml ) and h2o ( 4.5 ml ) , the solution 
 was then treated with ddq ( 410 mg , 1.8 mmol ) for 4 h. the title compound 
 was purified by flash column chromatography on silica gel ( 10% ethyl 
 acetate in toluene ) to afford compound 20 ( 180 mg , 91% ) 
 as colorless oil . the spectroscopic data is in good agreement with 
 previously reported data.h nmr ( 500 mhz , cdcl3 )  7.36 ( d , j = 4.4 hz , 4h ) , 7.357.26 ( m , 1h ) , 6.35 ( dd , j = 6.2 , 1.5 hz , 1h ) , 4.85 ( dd , j = 6.1 , 2.2 hz , 
 1h ) , 4.71 ( d , j = 11.7 hz , 1h ) , 4.55 ( d , j = 11.8 hz , 1h ) , 4.05 ( dt , j = 7.1 , 1.9 
 hz , 1h ) , 3.90 ( dq , j = 9.2 , 6.3 hz , 1h ) , 3.62 ( ddd , j = 9.3 , 7.0 , 3.6 hz , 1h ) , 2.19 ( d , j = 
 3.6 hz , 1h ) , 1.39 ( d , j = 6.4 hz , 3h ) . the title compound was prepared 
 according to procedure a using 21 ( 250 mg , 0.69 mmol ) 
 and -pinene ( 0.37 ml , 2.3 mmol ) 
 dissolved in dcm ( 58 ml ) and h2o ( 2.9 ml ) , the solution 
 was then treated with ddq ( 322 mg , 1.3 mmol ) for 2 h. the title compound 
 was purified by flash column chromatography on silica gel ( 30% ethyl 
 acetate in hexane ) to afford compound 22 ( 111 mg , 73% ) 
 as a pink - white solid . mp : 107108 c ; [  ] d = + 10.9 ( c 1.01 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  
 7.397.30 ( m , 5h ) , 6.336.32 ( dd , j = 6.0 , 1.4 hz , 1h ) , 4.82 ( d , j = 11.6 hz , 1h ) , 
 4.80 ( d , j = 11.6 hz , 1h ) , 4.70 ( dd , j = 6.0 , 2.3 hz , 1h ) , 4.374.33 ( m , 1h ) , 3.91 ( dq , j = 9.6 , 6.4 hz , 1h ) , 3.28 ( dd , j = 9.6 , 
 6.9 hz , 1h ) , 1.67 ( d , j = 5.6 hz , 1h ) , 1.41 ( d , j = 6.4 hz , 3h ) ; c nmr ( 126 mhz , cdcl3 )  144.7 , 138.3 , 128.6 , 127.9 , 103.1 , 82.5 , 74.3 , 74.1 , 70.0 , 
 17.6 ; hrms ( dart ) m / z : [ m  h ] calcd for c13h15o3 219.1027 ; found 219.1029 . the title compound was prepared according 
 to procedure b using 21 ( 250 mg , 0.69 mmol ) dissolved 
 in dcm ( 58 ml ) and h2o ( 2.9 ml ) , the solution was then 
 treated with ddq ( 322 mg , 1.3 mmol ) for 2 h. the title compound was 
 purified by flash column chromatography on silica gel ( 30% ethyl acetate 
 in hexane ) to afford a white solid . this solid was dissolved in pyridine 
 ( 1.2 ml ) , and treated with 4-dimethylaminopyridine ( 2 mg , 0.01 mmol ) 
 followed by dropwise addition of acetic anhydride ( 0.05 ml , 0.58 mmol ) . 
 after stirring for 3 h , the reaction mixture was concentrated in vacuo and azeotroped with toluene ( 2  25 ml ) . the 
 title compound was purified by flash column chromatography on silica 
 gel ( 20% ethyl acetate in hexane ) to afford compound 32 ( 75 mg , 60% over 2 steps 10:1 : ) as yellow oil . [  ] d = + 79.9 ( c 1.07 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  
 7.407.27 ( m , 5h ) , 6.21 ( s , 1h ) , 6.18 ( d , j = 9.7 hz , 1h ) , 5.78 ( ddd , j = 10.3 , 2.9 , 1.9 hz , 
 1h ) , 4.69 ( d , j = 11.5 hz , 1h ) , 4.57 ( d , j = 11.5 hz , 1h ) , 3.90 ( dq , j = 9.0 , 6.2 
 hz , 1h ) , 3.73 ( dq , j = 9.0 , 1.7 hz , 1h ) , 2.08 ( s , 
 3h ) , 1.32 ( d , j = 6.2 hz , 3h ) ; c nmr 
 ( 126 mhz , cdcl3 )  170.3 , 137.9 , 132.1 , 128.6 , 128.1 , 
 128.0 , 124.9 , 88.9 , 75.8 , 71.5 , 68.4 , 21.4 , 18.3 ; lrms ( esi ) m / z : [ m+na ] calcd for c15h18nao4 285.29 ; found 285.09 ; hrms 
 ( dart ) m / z : [ m - oac ] calcd for c13h15o2 203.1067 ; found 
 203.1085 . sodium hydride ( 60% 
 in mineral oil , 80 mg , 1.9 mmol ) and tetrabutylammonium iodide ( 48 
 mg , 0.13 mmol ) were suspended in dmf ( 10 ml ) . the suspension was cooled 
 to 0 c and treated with a solution of 4(21 ) ( 250 mg , 0.67 mmol ) in dmf ( 3 ml ) , while additional 
 dmf ( 3 ml ) was simultaneously added . after the mixture was stirred 
 for 10 min at 0 c , 2-(bromomethyl)-naphthalene ( 287 mg , 1.30 
 mmol ) in 4 ml dmf was added dropwise to the mixture and the reaction was then allowed to warm to room temperature . after being stirred 
 for 2 h , the reaction mixture was quenched with saturated aqueous 
 nh4cl and extracted three times with diethyl ether . the 
 pooled organic layers were washed with water and brine , and then dried 
 over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography 
 on silica gel ( 20% ethyl acetate in hexanes ) to afford compound 3 ( 336 mg , 98% ) as a white solid . the spectroscopic data is 
 in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 )  7.867.74 
 ( m , 4h ) , 7.547.44 ( m , 5h ) , 7.447.27 ( m , 8h ) , 5.55 
 ( s , 1h ) , 5.02 ( d , j = 12.3 hz , 1h ) , 4.94 ( d , j = 11.2 hz , 1h ) , 4.87 ( d , j = 11.8 hz , 
 2h ) , 4.59 ( d , j = 3.7 hz , 1h ) , 4.25 ( dd , j = 10.2 , 4.9 hz , 1h ) , 4.08 ( t , j = 9.3 
 hz , 1h ) , 3.83 ( td , j = 10.0 , 4.8 hz , 1h ) , 3.69 ( t , j = 10.3 hz , 1h ) , 3.643.56 ( m , 2h ) , 3.41 ( s , 3h ) . sodium hydride ( 60% 
 in mineral oil , 160 mg , 3.9 mmol ) and tetrabutylammonium iodide ( 96 
 mg , 0.26 mmol ) were suspended in dmf ( 6 ml ) . the suspension was cooled 
 to 0 c and treated with a solution of 6(21 ) ( 0.5 g , 1.3 mmol ) in dmf ( 3 ml ) , while additional 
 dmf ( 3 ml ) was simultaneously added . after the mixture was stirred 
 for 10 min at 0 c , 2-(bromomethyl)naphthalene ( 574 mg , 2.6 mmol ) 
 in 3 ml dmf was added dropwise to the mixture and the reaction was 
 then allowed to warm to room temperature . after being stirred for 
 2 h , the reaction mixture was quenched with saturated aqueous nh4cl and extracted three times with diethyl ether . the pooled 
 organic layers were washed with water and brine , and then dried over 
 na2so4 , filtered , and concentrated in 
 vacuo . the residue was purified by flash column chromatography 
 on silica gel ( 10% ethyl acetate in hexanes ) to afford compound 5 ( 656 mg , 98% ) as a white solid . the spectroscopic data is 
 in good agreement with previously reported data.h nmr ( 500 mhz , cdcl3 )  7.847.74 
 ( m , 3h ) , 7.737.67 ( m , 1h ) , 7.547.26 ( m , 13h ) , 5.57 
 ( s , 1h ) , 5.07 ( d , j = 11.6 hz , 1h ) , 5.00 ( d , j = 11.6 hz , 1h ) , 4.88 ( d , j = 12.1 hz , 
 1h ) , 4.73 ( d , j = 12.2 hz , 1h ) , 4.61 ( d , j = 3.7 hz , 1h ) , 4.27 ( dd , j = 10.2 , 4.8 
 hz , 1h ) , 4.10 ( t , j = 9.3 hz , 1h ) , 3.84 ( td , j = 9.9 , 4.8 hz , 1h ) , 3.72 ( t , j = 10.3 
 hz , 1h ) , 3.64 ( t , j = 9.4 hz , 1h ) , 3.59 ( dd , j = 9.3 , 3.8 hz , 1h ) , 3.41 ( s , 3h ) . synthesis of compound 24 was performed using procedures adapted from chan et al . a solution of 23(26 ) ( 3.43 g , 13 mmol ) in pyridine ( 21 ml ) was cooled to 0 c 
 and treated dropwise with pivaloyl chloride ( 8.5 ml , 69 mmol ) . the 
 reaction was then allowed to warm to room temperature and stirred 
 overnight . the mixture was then diluted with ethyl acetate and washed 
 with dilute aqueous hcl solution , saturated nahco3 solution , 
 and brine . the residue 
 was purified by flash column chromatography on silica gel ( 25% ethyl 
 acetate in hexanes ) to afford compound 24 ( 4.46 g , 97% ) 
 as a white solid . mp : 5455 c ; [  ] d = + 12.9 ( c = 1.4 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) :  5.00 ( dd , j = 10.2 , 7.3 hz , 1h ) , 4.32 ( d , j = 10.2 
 hz , 1h ) , 4.13 ( dd , j = 7.2 , 5.4 hz , 1h ) , 4.06 ( dd , j = 5.3 , 2.0 hz , 1h ) , 3.87 ( td , j = 6.5 , 
 1.9 hz , 1h ) , 2.762.69 ( m , 1h ) , 2.682.62 ( m , 1h ) , 1.57 
 ( s , 3h ) , 1.42 ( d , j = 6.5 hz , 3h ) , 1.36 ( s , 3h ) , 
 1.24 ( d , j = 2.5 hz , 3h ) , 1.23 ( s , 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  177.1 , 110.1 , 82.3 , 76.8 , 
 76.5 , 72.7 , 71.0 , 38.7 , 27.9 , 26.5 , 26.4 , 23.6 , 16.9 , 14.8 ; lrms ( esi ) m / z : [ m+na ] calcd for c16h28o5sna 355.16 ; found 355.27 ; hrms 
 ( dart ) m / z : [ m+nh4 ] calcd for c16h32no5s 350.1996 ; 
 found 350.2002 . synthesis of compound 25 was 
 performed using procedures adapted from van boom et al . a solution of 24 ( 2.79 g , 8.4 mmol ) 
 in acetic acid ( 41 ml ) and water ( 10 ml ) was refluxed at 110 c 
 for 24 h. the reaction mixture was cooled to room temperature . upon 
 cooling , the pooled organic layers were washed with brine , dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography on silica 
 gel ( 30% ethyl acetate in hexanes ) to afford compound 25 ( 1.56 g , 64% ) as an amorphous solid . [  ] d = 23.7 ( c = 1.02 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  4.91 ( t , j = 9.6 hz , 1h ) , 4.41 ( d , j = 10.0 hz , 
 1h ) , 3.78 ( ddd , j = 6.0 , 3.5 , 1.1 hz , 1h ) , 3.723.63 
 ( m , 2h ) , 2.96 ( d , j = 7.5 hz , 1h ) , 2.792.61 
 ( m , 2h ) , 2.25 ( d , j = 5.9 hz , 1h ) , 1.37 ( d , j = 6.5 hz , 3h ) , 1.27 ( t , j = 7.4 hz , 3h ) , 
 1.25 ( s , 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  
 179.0 , 82.9 , 74.6 , 74.2 , 72.1 , 71.4 , 38.9 , 27.1 , 23.9 , 16.6 , 15.0 ; 
 lrms ( esi ) m / z : [ m+na ] calcd for c13h24o5sna 315.12 ; found 
 314.82 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c13h28no5s 310.1683 ; found 310.1693 . synthesis of 
 compound 26 was performed using procedures adapted from 
 takahashi et al . compound 25 ( 1 g , 3.4 mmol ) and bu2sno ( 0.93 g , 3.7 mmol ) were suspended 
 in toluene ( 33 ml ) at room temperature . tetrabutylammonium iodide ( 0.25 
 g , 0.68 mmol ) and 2-(bromomethyl)naphthylene ( 1.1 g , 5.1 mmol ) were 
 added to the reaction mixture at room temperature . the reaction was 
 returned to reflux , stirred for 3 h , allowed to cool to room temperature , 
 and concentrated in vacuo . the crude residue was 
 purified by flash column chromatography on silica gel ( 2030% 
 ethyl acetate in hexanes ) to afford compound 26 ( 680 
 mg , 46% ) as an amorphous solid . [  ] d = 20.8 ( c = 1.06 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.857.82 ( m , 3h ) , 
 7.74 ( s , 1h ) , 7.517.41 ( m , 3h ) , 5.29 ( t , j = 9.7 hz , 1h ) , 4.804.79 ( m , 2h ) , 4.33 ( d , j = 10.0 hz , 1h ) , 3.85 ( s , 1h ) , 3.62 ( dd , j = 9.4 , 
 3.3 hz , 1h ) , 3.58 ( d , j = 6.3 hz , 1h ) , 2.792.64 
 ( m , 2h ) , 2.43 ( s , 1h ) , 1.36 ( d , j = 6.5 hz , 3h ) , 
 1.261.21 ( m , 12h ) ; c nmr ( 125 mhz , cdcl3 ) :  177.2 , 134.9 , 133.3 , 133.2 , 128.6 , 128.0 , 127.9 , 126.6 , 
 126.5 , 126.3 , 125.6 , 83.2 , 80.3 , 74.6 , 72.1 , 69.4 , 68.5 , 38.9 , 27.4 , 
 23.4 , 16.8 , 14.9 ; lrms ( esi ) m / z : [ m+na ] calcd for c24h32o5sna 455.19 ; found 455.64 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c24h36no5s 450.2309 ; found 450.2302 . a solution of 26 ( 540 mg , 1.2 mmol ) and sodium hydride ( 60% in mineral oil , 
 190 mg , 4.7 mmol ) in dmf ( 8 ml ) was cooled to 0 c and treated 
 dropwise with benzyl bromide ( 0.29 ml , 2.4 mmol ) ; the reaction was 
 then allowed to warm to room temperature for 1 h. the reaction mixture 
 was quenched with saturated aqueous nh4cl solution . the 
 reaction was diluted with et2o and h2o , and 
 extracted 3 times with et2o . the pooled organic layers 
 were washed two times with h2o and brine , dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography on silica 
 gel ( 1015% ethyl acetate in hexanes ) to afford compound 11 ( 462.8 mg , 74% ) as a white powder . mp : 9798 c ; 
 [  ] d = 4.0 ( c = 0.97 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) :  7.857.81 ( m , 3h ) , 7.76 ( s , 1h ) , 7.507.48 
 ( m , 2h ) , 7.447.42 ( m , 1h ) , 7.347.24 ( m , 5h ) , 5.49 
 ( t , j = 6.5 hz , 1h ) , 5.00 ( d , j = 
 12.0 hz , 1h ) , 4.79 ( s , 2h ) , 4.68 ( d , j = 11.5 hz , 
 1h ) , 4.35 ( d , j = 10.0 hz , 1h ) , 3.67 ( d , j = 2.7 hz , 1h ) , 3.65 ( s , 1h ) , 3.54 ( q , j = 6.4 hz , 1h ) , 2.792.72 ( m , 1h ) , 2.712.64 ( m , 1h ) , 
 1.251.22 ( m , 15h ) ; c nmr ( 125 mhz , cdcl3 ) :  177.1 , 138.7 , 135.6 , 133.4 , 133.1 , 128.4 , 128.3 , 128.2 , 
 128.0 , 127.9 , 127.6 , 126.4 , 126.2 , 126.1 , 125.6 , 83.5 , 82.5 , 76.1 , 
 75.1 , 74.5 , 72.8 , 69.3 , 38.9 , 27.4 , 23.4 , 17.4 , 14.9 ; lrms ( esi ) m / z : [ m+na ] calcd for c31h38so5na 545.23 ; found 545.35 ; hrms 
 ( dart ) m / z : [ m+nh4 ] calcd for c31h42nso5 540.2778 ; 
 found 540.2783 . synthesis of compound 28 was 
 performed using procedures adapted from van boom et al . a solution of 27(27 ) ( 1.92 g , 5.0 mmol ) in acetic acid ( 24 ml ) and water ( 6 
 ml ) was refluxed at 110 c for 2 h. the reaction mixture was 
 then allowed to cool to room temperature . upon cooling the mixture was washed 
 with saturated nahco3 solution and brine , dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography on silica 
 gel ( 50% ethyl acetate in hexanes ) to afford compound 28 ( 1.64 g , 96% ) as a white powder . mp : 149150 c ; [  ] d = 11.0 ( c = 1.22 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.537.45 
 ( m , 2h ) , 7.367.28 ( m , 3h ) , 4.88 ( t , j = 9.6 
 hz , 1h ) , 4.64 ( d , j = 10.1 hz , 1h ) , 3.77 ( ddd , j = 6.1 , 3.4 , 1.0 hz , 1h ) , 3.743.64 ( m , 2h ) , 2.97 
 ( d , j = 7.5 hz , 1h ) , 2.15 ( d , j = 
 6.1 hz , 1h ) , 1.39 ( d , j = 6.5 hz , 3h ) , 1.28 ( s , 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  179.0 , 133.2 , 
 132.5 , 129.1 , 128.1 , 86.2 , 74.6 , 74.5 , 72.1 , 71.4 , 39.1 , 27.3 , 16.8 ; 
 lrms ( esi ) m / z : [ m+na ] calcd for c17h24o5sna 363.12 ; found 
 363.27 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c17h28no5s 358.1683 ; found 358.1682 . compound 28 ( 250 mg , 
 0.74 mmol ) and bu2sno ( 200 mg , 0.81 mmol ) were suspended 
 in toluene ( 7 ml ) at room temperature . tetrabutylammonium iodide ( 54.3 
 mg , 0.15 mmol ) and benzyl bromide ( 0.13 ml , 1.1 mmol ) were added to 
 the reaction mixture at room temperature . the reaction was returned 
 to reflux , stirred for 3 h , the reaction mixture was allowed to cool 
 to room temperature , and then was concentrated in vacuo . the crude product was purified by flash column chromatography on 
 silica gel ( 30% ethyl acetate in hexanes ) to afford 14 ( 287.5 mg , 91% ) as an amorphous solid . [  ] d = + 5.5 ( c = 0.95 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) :  7.507.48 ( m , 2h ) , 
 7.347.26 ( m , 8h ) , 5.23 ( t , j = 9.8 hz , 1h ) , 
 4.664.58 ( m , 3h ) , 3.84 ( t , j = 2.5 hz , 1h ) , 
 3.623.57 ( m , 2h ) , 2.38 ( s , 1h ) , 1.40 ( d , j = 6.5 hz , 3h ) , 1.24 ( s , 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  177.0 , 137.4 , 133.9 , 132.2 , 128.9 , 128.7 , 128.2 , 
 127.8 , 127.7 , 86.9 , 80.4 , 74.5 , 71.9 , 69.2 , 68.6 , 38.9 , 27.3 , 16.9 ; 
 lrms ( esi ) m / z : [ m+na ] calcd for c24h30o5sna 453.17 ; found 
 453.36 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c24h34no5s 448.2152 ; found 448.2155 . a solution of 14 ( 1.6 g , 3.7 mmol ) and sodium hydride ( 60% in mineral oil , 
 0.46 g , 11 mmol ) in dmf ( 8.6 ml ) was cooled to 0 c and treated 
 with 2-(bromomethyl)naphthylene ( 1.6 g , 7.5 mmol ) , and then the reaction 
 was allowed to warm to room temperature . after being stirred overnight , 
 the reaction mixture was quenched using saturated nh4cl 
 aqueous solution . the reaction was diluted with et2o and 
 h2o and extracted 3 times with et2o . the pooled 
 organic layer was washed two times with h2o then washed 
 with brine . the pooled organic layers were dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by column chromatography on silica gel 
 ( 100% toluene ) to afford compound 13 ( 1.97 g , 91% ) as 
 a white powder . mp : 8687 c ; [  ] d = + 4.4 ( c = 1.29 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.827.75 ( m , 3h ) , 
 7.67 ( s , 1h ) , 7.507.45 ( m , 5h ) , 7.357.30 ( m , 5h ) , 
 7.267.17 ( m , 3h ) , 5.51 ( t , j = 9.8 hz , 1h ) , 
 5.11 ( d , j = 11.9 hz , 1h ) , 4.82 ( d , j = 11.9 hz , 1h ) , 4.694.59 ( m , 3h ) , 3.68 ( d , j = 2.8 hz , 1h ) , 3.64 ( dd , j = 9.6 , 2.7 hz , 1h ) , 
 3.56 ( q , j = 6.9 hz , 1h ) , 1.27 ( d , j = 6.3 hz , 3h ) , 1.24 ( s , 9h ) ; c nmr ( 125 mhz , cdcl3 ) :  176.8 , 137.9 , 135.9 , 134.3 , 133.1 , 133.0 , 131.8 , 
 131.5 , 128.7 , 128.5 , 127.9 , 127.8 , 127.7 , 127.6 , 127.4 , 126.9 , 126.5 , 
 125.9 , 125.8 , 87.1 , 82.6 , 75.4 , 74.9 , 74.3 , 72.7 , 69.3 , 38.8 , 27.2 , 
 17.4 ; lrms ( esi ) m / z : [ m+na ] calcd for c35h38o5sna 593.23 ; 
 found 593.36 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c35h42no5s 588.2778 ; 
 found 588.2785 . sodium hydride ( 60% by weight , 1 g , 27 
 mmol ) and tetrabutylammonium iodide ( 664 mg , 1.8 mmol ) were suspended 
 in dmf ( 38 ml ) . the suspension was cooled to 0 c and treated 
 with a solution of 20(25 ) ( 2 
 g , 9.0 mmol ) in dmf ( 15 ml ) , while additional dmf ( 15 ml ) was simultaneously 
 added . after the mixture was stirred for 10 min at 0 c , 2-(bromomethyl)naphthalene 
 ( 3.9 g , 18 mmol ) in 10 ml dmf was added dropwise to the mixture and 
 the reaction was then allowed to warm to room temperature . after being 
 stirred for 2 h , the reaction mixture was quenched with saturated 
 aqueous nh4cl and extracted three times with diethyl ether . the pooled organic layers were washed with water and brine , and then 
 dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography 
 on silica gel ( 2% ethyl acetate in hexanes ) to afford compound 19 ( 2.9 g , 90% ) as a white powder . mp : 6061 c ; 
 [  ] d = 40.1 ( c = 1.32 , ch2cl2 ) ; h nmr ( 500 mhz , 
 cdcl3 )  7.877.78 ( m , 3h ) , 7.75 ( s , 1h ) , 
 7.47 ( ht , j = 5.3 , 2.5 hz , 3h ) , 7.34 ( dt , j = 6.9 , 2.1 hz , 3h ) , 7.327.22 ( m , 2h ) , 6.37 ( d , j = 6.0 hz , 1h ) , 5.03 ( dd , j = 11.9 , 4.1 
 hz , 1h ) , 4.914.83 ( m , 2h ) , 4.67 ( dt , j = 
 12.3 , 2.9 hz , 1h ) , 4.58 ( dd , j = 11.6 , 1.9 hz , 1h ) , 
 4.26 ( dd , j = 6.9 , 2.9 , 2.3 hz , 1h ) , 4.043.94 
 ( m , 1h ) , 3.54 ( ddd , j = 8.7 , 6.4 , 1.9 hz , 1h ) , 1.40 
 ( dd , j = 6.4 , 1.9 hz , 3h ) ; c nmr ( 125 
 mhz , cdcl3 )  144.9 , 138.5 , 135.8 , 133.4 , 133.1 , 
 128.5 , 128.3 , 128.0 , 127.9 , 127.8 , 127.7 , 126.8 , 126.2 , 126.1 , 126.0 , 
 100.2 , 79.5 , 76.6 , 74.2 , 74.1 , 70.6 , 17.7 ; lrms ( esi ) m / z : [ m+nh4 ] calcd for c24h28no3 378.45 ; found 378.02 ; hrms ( dart ) m / z : [ m+nh4 ] calcd 
 for c24h28no3 378.2064 ; found 378.2076 . sodium hydride ( 60% in mineral oil , 738 
 mg , 18 mmol ) and tetrabutylammonium iodide ( 679 mg , 1.8 mmol ) were 
 suspended in dmf ( 42 ml ) . the suspension was cooled to 0 c and 
 treated with a solution of 29(25 ) ( 2.5 g , 9.2 mmol ) in dmf ( 10 ml ) , while additional dmf ( 10 ml ) was 
 simultaneously added . after the mixture was stirred for 10 min at 
 0 c , benzyl bromide ( 2.1 ml , 18 mmol ) was added dropwise to 
 the mixture and the reaction was then allowed to warm to room temperature . 
 after being stirred for 3 h , the reaction mixture was quenched with 
 saturated aqueous nh4cl and extracted three times with 
 diethyl ether . the pooled organic layers were washed with water and 
 brine , and then dried over na2so4 , filtered , 
 and concentrated in vacuo . the residue was purified 
 by flash column chromatography on silica gel ( 2% ethyl acetate in 
 hexanes ) and afforded compound 21 ( 2.8 g , 87% ) as an 
 amorphous solid : [  ] d = 54.4 
 ( c = 1.14 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.907.67 ( m , 4h ) , 
 7.577.37 ( m , 3h ) , 7.377.17 ( m , 5h ) , 6.37 ( d , j = 6.1 , 1.4 hz , 1h ) , 4.984.83 ( m , 2h ) , 4.82 ( d , j = 12.0 hz , 1h ) , 4.764.69 ( m , 2h ) , 4.27 ( dd , j = 6.6 , 1.4 hz , 1h ) , 3.96 ( dq , j = 9.1 , 
 6.5 hz , 1h ) , 3.52 ( dd , j = 9.0 , 6.5 hz , 1h ) , 1.39 
 ( d , j = 6.4 hz , 3h ) ; c nmr ( 125 mhz , 
 cdcl3 )  144.9 , 138.3 , 136.0 , 133.0 , , 128.4 , 128.2 , 
 128.1 , 128.0 , 127.9 , 127.8 , 126.5 , 126.5 , 126.2 , 126.0 , 125.9 , 100.3 , 
 79.7 , 76.6 , 74.1 , 70.8 , 17.6 ; ; lrms ( esi ) m / z : [ m+na ] calcd for c24h24o3na 383.16 ; found 383.18 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c24h28no3 378.2064 ; found 378.2059 . synthesis of compound 30 was 
 performed using procedures adapted from blumenstein et al . to a solution of 19 ( 1.5 g , 5.2 
 mmol ) in thf ( 20 ml ) , ph3hbr ( 361 mg , 1.0 mmol ) was 
 added to the reaction and allowed to stir at room temperature . after 
 10 min , h2o ( 0.47 ml , 26 mmol ) was added to the reaction . the reaction was stirred for 4 h. the reaction was quenched with saturated , 
 aqueous nahco3 , diluted with ethyl acetate and water , and 
 extracted 3 times with ethyl acetate . the pooled organic layer was 
 washed with h2o and brine , dried over na2so4 , filtered , and concentrated in vacuo . the 
 residue was purified by flash column chromatography on silica gel 
 ( 25% ethyl acetate in hexanes ) to afford compound 30 ( 1.8 
 g , 94% ) as a white powder . mp : 150151 c ; [  ] d = + 14.8 ( c = 1.05 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.867.74 ( m , 4h ) , 7.517.42 ( m , 3h ) , 7.397.25 
 ( m , 5h ) , 5.35 ( d , j = 3.7 hz , 1h ) , 5.11 ( d , j = 11.2 hz , 1h ) , 4.82 ( d , j = 10.8 hz , 
 1h ) , 4.734.63 ( m , 2h ) , 4.093.97 ( m , 2h ) , 3.20 ( dd , j = 19.2 , 0.9 hz , 1h ) , 2.382.30 ( m , 2h ) , 1.70 ( ddd , j = 13.2 , 11.2 , 3.6 , 2.2 hz , 1h ) , 1.30 ( d , j = 6.3 hz , 3h ) ; c nmr ( 125 mhz , cdcl3 )  
 138.7 , 136.1 , 133.39 , 133.0 , 128.6 , 128.5 , 128.2 , 128.1 , 128.0 , 127.8 , 
 127.77 , 127.76 , 127.7 , 126.8 , 126.7 , 126.2 , 126.1 , 126.0 , 125.9 , 93.9 , 
 92.1 , 84.4 , 83.5 , 79.1 , 76.9 , 75.3 , 75.28 , 71.9 , 71.6 , 71.6 , 67.5 , 
 53.5 , 38.5 , 35.9 , 18.4 , 18.38 ; lrms ( esi ) m / z : [ m+na ] calcd for c24h26o4na 401.17 ; found 401.19 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c24h30no4 396.2169 ; found 396.2157 . synthesis of compound 31 was 
 performed using procedures adapted from blumenstein et al . to a solution of 21 ( 890 mg , 2.4 
 mmol ) in thf ( 10 ml ) , ph3hbr ( 168 mg , 0.49 mmol ) 
 was added to the reaction and allowed to stir at room temperature . after 10 min , h2o ( 0.21 ml , 12 mmol ) was added to the reaction . the reaction was stirred for 6 h. the reaction was quenched with saturated , 
 aqueous nahco3 , diluted with ethyl acetate and water , and 
 extracted 3 times with ethyl acetate . the pooled organic layers were 
 washed with h2o and brine , dried over na2so4 , filtered , and concentrated in vacuo . the 
 residue was purified by flash column chromatography on silica gel 
 ( 25% ethyl acetate in hexanes ) to afford compound 31 ( 852 
 mg , 93% ) as a white powder . mp : 9798 c ; [  ] d = + 15.0 ( c = 1.15 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.857.73 ( m , 4h ) , 7.497.42 ( m , 3h ) , 7.377.26 
 ( m , 5h ) , 5.35 ( s , 1h ) , 4.99 ( d , j = 11.0 hz , 1h ) , 
 4.884.74 ( m , 2h ) , 4.70 ( d , j = 11.0 hz , 1h ) , 
 4.163.95 ( m , 2h ) , 3.17 ( t , j = 9.1 hz , 1h ) , 
 2.35 ( dd , j = 24.0 , 7.9 hz , 1h ) , 1.771.67 
 ( m , 1h ) , 1.29 ( d , j = 6.2 hz , 3h ) ; c 
 nmr ( 125 mhz , cdcl3 )  138.7 , 136.3 , 133.5 , 133.1 , 
 128.6 , 128.5 , 128.4 , 128.2 , 128.1 , 128.07 , 128.03 , 128.0 , 127.8 , 127.7 , 
 126.6 , 126.4 , 126.3 , 126.2 , 126.1 , 125.9 , 93.9 , 92.2 , 84.5 , 83.6 , 
 79.0 , 77.4 , 77.0 , 75.4 , 75.3 , 72.0 , 71.7 , 67.6 , 38.6 , 36.0 , 18.4 , 
 18.3 ; lrms ( esi ) m / z : [ m+na ] calcd for c24h26o4na 401.17 ; 
 found 401.18 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c24h30no4 396.2169 ; found 396.2155 . a solution of donor 30 ( 142 
 mg , 0.375 mmol ) and 2,4,6-tritert - butylpyrimidine 
 ( ttbp , 74 mg , 0.375 mmol ) in 3 ml thf was cooled to 78 c 
 and treated dropwise with potassium hexamethyldisilazane ( 1 m in thf , 
 0.375 ml , 0.375 mmol ) . after 15 min , a solution of p - toluenesulfonic anhydride ( 122 mg , 0.375 mmol ) in 2 ml thf was added 
 slowly to the reaction . the solution was maintained at 78 
 c for 30 min . meanwhile in a separate flask , 4-methoxyphenol 
 ( 31 mg , 0.250 mmol ) was dissolved in 2 ml thf , cooled to 78 
 c , and treated with potassium hexamethyldisilazane ( 1 m in thf , 
 0.25 ml , 0.25 mmol ) . after 30 min , this solution was transferred dropwise 
 by syringe to the primary reaction vessel . the reaction mixture was 
 then allowed to gradually warm to room temperature over the course 
 of 4 h. the reaction was quenched with 0.3 ml of saturated , aqueous 
 nh4cl , diluted with water , and extracted 3 times with diethyl 
 ether . the pooled organic layers were washed with h2o and 
 brine , dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography 
 on silica gel ( 10% ethyl acetate in hexanes ) to afford 17 as a single -anomer ( 84 mg , 54% ) as a white powder . mp : 9394 
 c ; [  ] d = 31.2 ( c = 1.12 , ch2cl2 ) ; h nmr 
 ( 500 mhz , cdcl3 )  7.867.75 ( m , 4h ) , 7.527.43 
 ( m , 3h ) , 7.417.26 ( m , 5h ) , 6.986.92 ( m , 2h ) , 6.846.78 
 ( m , 2h ) , 5.13 ( d , j = 11.1 hz , 1h ) , 4.97 ( dd , j = 9.9 , 2.1 hz , 1h ) , 4.85 ( d , j = 11.1 
 hz , 1h ) , 4.75 ( d , j = 11.7 hz , 1h ) , 4.66 ( d , j = 11.7 hz , 1h ) , 3.76 ( s , 3h ) , 3.763.69 ( m , 1h ) , 
 3.543.45 ( m , 1h ) , 3.28 ( t , j = 8.9 hz , 1h ) , 
 2.53 ( dd , j = 12.5 , 5.0 hz , 1h ) , 1.90 ( dd , j = 12.0 , 9.8 hz , 1h ) , 1.39 ( d , j = 6.2 
 hz , 3h ) ; c nmr ( 125 mhz , cdcl3 )  155.1 , 
 151.4 , 138.4 , 135.9 , 133.4 , 133.1 , 128.6 , 128.3 , 128.1 , 127.9 , 127.8 , 
 126.9 , 126.22 , 126.2 , 118.0 , 114.6 , 98.5 , 83.6 , 79.2 , 75.5 , 71.7 , 
 55.8 , 37.0 , 18.5 ; lrms ( esi ) m / z : [ m+na ] calcd for c31h32o5na 507.21 ; found 507.26 ; hrms ( dart ) m / z : [ m+nh4 ] calcd for c31h36no5 502.2588 ; found 502.2592 . a solution of donor 31 ( 138 mg , 0.36 mmol ) and 2,4,6-tritert - butylpyrimidine 
 ( ttbp , 89 mg , 0.36 mmol ) in 5 ml thf was cooled to 78 c 
 and treated dropwise with potassium hexamethyldisilazane ( 1 m in thf , 
 0.36 ml , 0.36 mmol ) . after 15 min , a solution of p - toluenesulfonic 
 anhydride ( 117 mg , 0.36 mmol ) in 2 ml thf was added slowly to the 
 reaction . meanwhile in a separate flask , the acceptor 18 ( 84 
 mg , 0.24 mmol ) was dissolved in 2 ml thf , cooled to 78 c , 
 and treated with potassium hexamethyldisilazane ( 1 m in thf , 0.24 
 ml , 0.24 mmol ) . after 30 min , this solution was transferred dropwise 
 by syringe to the primary reaction vessel . the reaction mixture was 
 then allowed to gradually warm to room temperature over the course 
 of 4.5 h. the reaction was quenched with 0.3 ml of saturated , aqueous 
 nh4cl , diluted with water , and extracted 3 times with dcm . the pooled organic layers were washed with h2o , dried over 
 na2so4 , filtered , and concentrated in 
 vacuo . the residue was purified by flash column chromatography 
 on silica gel ( 15% ethyl acetate in hexanes ) to afford 1 as a single -anomer ( 127 mg , 75% ) as a white powder . mp : 
 115116 c ; [  ] d = 33.4 
 ( c = 1.28 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.867.72 ( m , 4h ) , 
 7.497.43 ( m , 3h ) , 7.407.22 ( m , 10h ) , 6.94 ( d , j = 9.4 hz , 2h ) , 6.80 ( d , j = 9.7 hz , 2h ) , 
 5.004.91 ( m , 2h ) , 4.834.63 ( m , 6h ) , 3.76 ( s , 3h ) , 
 3.693.59 ( m , 2h ) , 3.493.39 ( m , 1h ) , 3.383.25 
 ( m , 2h ) , 3.15 ( t , j = 9.0 hz , 1h ) , 2.45 ( ddd , j = 12.6 , 5.2 , 2.1 hz , 1h ) , 2.39 ( ddd , j = 21.7 , 8.3 , 4.0 hz , 1h ) , 1.86 ( td , j = 12.2 , 10.0 
 hz , 1h ) , 1.63 ( td , j = 12.1 , 9.9 hz , 1h ) , 1.34 ( d , j = 8.9 hz , 3h ) , 1.30 ( d , j = 6.1 hz , 3h ) . c nmr ( 125 mhz , cdcl3 )  155.2 , 151.3 , 138.7 , 
 138.6 , 136.0 , 128.5 , 128.4 , 128.3 , 128.2 , 128.0 , 127.9 , 127.8 , 127.7 , 
 127.6 , 126.5 , 126.3 , 126.0 , 125.9 , 118.1 , 114.6 , 100.3 , 98.5 , 83.9 , 
 82.4 , 79.3 , 77.8 , 75.4 , 72.0 , 71.8 , 71.4 , 55.8 , 37.6 , 37.1 , 18.6 , 
 18.4 ; lrms ( esi ) m / z : [ m+na ] calcd for c44h48o8na 727.32 ; 
 found 727.45 ; hrms ( esi ) m / z : [ m+nh4 ] calcd for c44h52no8 722.3687 ; found 722.3695 . to a solution of 8(22 ) ( 1 g , 2.6 mmol ) in dmf ( 12 
 ml ) at 0 c , sodium hydride ( 60% in mineral oil , 322 mg , 8 mmol ) 
 was added . after the mixture was stirred for 10 min at 0 c , 
 2-(bromomethyl)naphthalene ( 1.1 g , 5.2 mmol ) in 6 ml dmf was added 
 dropwise to the mixture and the reaction was then allowed to warm 
 to room temperature . after being stirred for 16 h , the reaction mixture 
 was quenched with saturated aqueous nh4cl and extracted 
 three times with diethyl ether . the pooled organic layers were washed 
 with water and brine , dried over na2so4 , filtered , 
 and concentrated in vacuo . the residue was purified 
 by flash column chromatography on silica gel ( 15% ethyl acetate in 
 hexanes ) to afford compound 7 ( 900 mg , 70% ) as a white 
 solid . mp : 154155 c ; [  ] d = 15.5 ( c 1.07 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 )  7.857.75 
 ( m , 4h ) , 7.527.44 ( m , 5h ) , 7.447.27 ( s , 8h ) , 5.58 
 ( s , 1h ) , 5.03 ( d , j = 11.2 hz , 1h ) , 4.93 ( t , j = 6.0 , 5.3 hz , 2h ) , 4.82 ( d , j = 11.4 
 hz , 1h ) , 4.47 ( d , j = 7.6 hz , 1h ) , 4.38 ( dd , j = 10.5 , 5.0 hz , 1h ) , 3.79 ( q , j = 9.5 , 
 8.6 hz , 2h ) , 3.70 ( t , j = 9.3 hz , 1h ) , 3.61 ( s , 3h ) , 
 3.51 ( t , j = 8.2 hz , 1h ) , 3.44 ( td , j = 9.7 , 5.0 hz , 1h ) ; c nmr ( 125 mhz , cdcl3 )  138.6 , 137.5 , 136.0 , 133.4 , 133.2 , 129.1 , 128.4 , 128.4 , 
 128.2 , 128.1 , 127.8 , 127.7 , 126.8 , 126.3 , 126.1 , 126.1 , 125.9 , 105.4 , 
 101.3 , 82.3 , 81.7 , 80.9 , 75.4 , 75.3 , 68.9 , 66.1 , 57.6 ; lrms ( esi ) m / z : [ m+na ] calcd for c32h32nao6 535.59 ; found 535.36 ; hrms 
 ( dart ) m / z : [ m+h ] calcd 
 for c32h33o6 513.2272 ; found 513.2281 . sodium hydride ( 60% 
 in mineral oil , 480 mg , 12 mmol ) and tetrabutylammonium iodide ( 295 
 mg , 0.8 mmol ) were suspended in dmf ( 18 ml ) . the suspension was cooled 
 to 0 c and treated with a solution of 10(23 ) ( 1.5 g , 4.0 mmol ) in dmf ( 9 ml ) , while additional 
 dmf ( 9 ml ) was simultaneously added . after the mixture was stirred 
 for 10 min at 0 c , 2-(bromomethyl)naphthalene ( 1.7 g , 8 mmol ) 
 in 9 ml dmf was added dropwise to the mixture and the reaction was 
 then allowed to warm to room temperature . after being stirred for 
 3 h , the reaction mixture was quenched with saturated aqueous nh4cl and extracted three times with diethyl ether . the pooled 
 organic layers were washed with water and brine , dried over na2so4 , filtered , and concentrated in vacuo . the residue was purified by flash column chromatography on silica 
 gel ( 15% ethyl acetate in hexanes ) to afford compound 9 ( 1.8 g , 87% ) as colorless foam . [  ] d = 14.6 ( c 1.16 , ch2cl2 ) ; h nmr ( 500 mhz , cdcl3 ) 7.877.76 
 ( m , 4h ) , 7.577.45 ( m , 5h ) , 7.427.25 ( m , 8h ) , 5.66 
 ( d , j = 2.7 hz , 1h ) , 4.94 ( q , j = 
 12.4 , 2.6 hz , 2h ) , 4.83 ( d , j = 12.2 , 2.9 hz , 1h ) , 
 4.72 ( s , 1h ) , 4.65 ( d , j = 12.3 , 2.7 hz , 1h ) , 4.334.23 
 ( m , 2h ) , 3.993.85 ( m , 3h ) , 3.79 ( td , j = 
 9.8 , 4.5 hz , 1h ) , 3.31 ( s , 3h ) ; c nmr ( 125 mhz , cdcl3 )  138.8 , 137.8 , 135.6 , 133.3 , 133.2 , 128.9 , 128.4 , 
 128.3 , 128.2 , 128.0 , 127.8 , 127.6 , 127.6 , 127.1 , 126.3 , 126.2 , 126.1 , 
 126.0 , 101.6 , 100.6 , 79.3 , 76.6 , 76.3 , 73.8 , 73.3 , 69.0 , 64.2 , 54.9 ; 
 lrms ( esi ) m / z : [ m+na ] calcd for c32h32nao6 535.59 ; found 
 535.36 ; hrms ( dart ) m / z : [ m  och3 ] calcd for c31h29o5 481.2010 ; found 481.2021 .
the 
 use of a combination of 2,3-dichloro-5,6-dicyano-1,4-benzoquinone 
 ( ddq ) and -pinene permits the removal of 2-naphthylmethyl ( nap ) 
 ether protecting groups on highly sensitive substrates . 
 the reaction 
 tolerates both acid and base sensitive protecting groups , and products 
 are afforded in 6896% yield . 
 the utility of the method is 
 demonstrated by the removal of the nap protecting groups on highly 
 sensitive 2,6-dideoxy - sugar disaccharides .