Next, the use of a 2-substituted pyrrolidine was examined. For this purpose, the 2-methyl substituted N-phenylpyrrolidine 1f was prepared and submitted to our standard reaction conditions. It afforded the desired bicyclic 3f containing a quaternary carbon at the bridgehead position in 40% yield. This result was surpassing our expectation since a difficult regioselectivity control was expected for the second step of the process, i.e. the conversion of 2f to 3f via 6-endo-trig cyclization. A study of this cyclization showed that 3f could be obtained from 2f in 66% isolated yield indicating that the desired α-amino-α-methyl radical R2f was preferentially formed over R2f'. This cyclization yield compared well with the non-methylated substrate 2a that afforded 3a in 77% isolated yield. Encouraged by these results, we then turned our attention to the preparation of the homotropane 9azabicyclo[3.3.1]nonane skeleton as well as higher [4.3.1]-analogues (Scheme 7). Piperidine derivatives proved in general to react slightly better than pyrrolidine derivatives. N-Phenylpiperidine 6a gave the cyclized product 8a in 67% yield (57% on 3 mmol scale) with an excellent level of diastereoselectivity (α/β > 20:1). The N-toluyl derivatives 8b-8d were obtained in similar yields and levels of diastereoselectivity. The electron rich N-p-anisyl derivatives in the presence of CsOPiv as a base required longer reaction time and afforded 8e in lower yield (32%). Aromatic rings substituted by electron releasing groups afforded the homotropanes 8f-8j in good yields and shorter reaction times in most cases. The p-ester substituted homotropane 8g was prepared 63% yield on 1 mmol scale and the p-pinacolboryl derivative 8j in 56% yield on 3 mmol scale. Gratifyingly, in all the scale-up experiments for 8a, 8g and 8j, the catalyst loading could be decreased to 0.5 mol%. The relative αconfiguration of 8g was confirmed by single crystal X-ray diffraction crystallography. Annulations starting from N-phenylmorpholine, N-phenylpiperazine and N-phenylthiomorpholine derivatives 6km provided the bicyclic amines 8k-m in good yields. Remarkably, no products arising from the ringopening of the piperazine 30 and thiomorpholine were observed. Finally, the reactivity of azepane derivatives were investigated. The N-phenyl derivative 6n gave the bicylic amine 8n in a modest 25% yield after 14h. When the reaction was stopped after 10 minutes, the allylated product 7n was obtained in 65% yield together with some cyclized product indicating that the 6-endo cyclization was probably the yield limiting step. This was confirmed by an independent cyclization attempt starting from 7n that afforded 8n in 24% yield after two hours, along with 9% unreacted 7n and some unidentified side products. The N-(p-methoxycarbonylphenyl) derivative 6o was also examined. After 9 h of reaction, only the allylated product 7o was formed in a low 25% yield and incomplete conversion. 2-Alkyl-3-ethoxycarbonyl substituted tropanes and homotropanes skeletons are expected to be accessible by using easily available acetylated Baylis-Hillman adducts. In order to test this hypothesis, ethyl 2-(1-acetoxyethyl)acrylate was prepared from the ethyl acrylate and acetaldehyde and reacted with N-(p-methoxycarbonylphenyl)piperidine 6g (Scheme 8). When 1.1 equivalent of the trap was employed under our standard reaction conditions, prolongated irradiation afforded a mixture of the desired tropane skeleton 10 together with mono-allylated piperidine 9 and the bis-allylated product. Using a 2.5 fold excess of the amine allowed for the formation of the bis-allylated product to be suppressed and, after 10 minutes of irradiation, the intermediate 9 was obtained in 73% yield and with a good E-stereoselectivity (E/Z 7:1). Recrystallization of 9 afforded a virtually diastereomerically pure product (E/Z > 20:1). Gratifyingly, under our optimized cyclization conditions the major E-9 afforded 10 in 66% yield and as a single diastereomer (dr > 20:1). However, despite the good results obtained for both steps separately, the one-pot process provided a mixture of 9 and 10. This mixture can be treated under the cyclization conditions to ultimately give the cyclized product 10 in 71% yield contaminated with a by-product, presumably a diastereomer. The diester 10 was converted to corresponding diol 11 whose relative configuration could be determined by single crystal X-ray diffraction crystallography (Scheme 8). The formation of the major diastereomers results presumably from a chair-like transition state as depicted in Scheme 8. Methoxyphenyl substituents can be removed under oxidative conditions using chemical oxidants such as cerium ammonium nitrate (CAN) or electrochemical methods. The cleavage of the N-p-MeOPh group of 3c and 8e was investigated first and proved to be problematic when an aqueous CAN solution was used as the quinone liberated during the process reacted with the liberated secondary amines.