stereochemical control. A number of total syntheses have made use of macrocyclic stereocontrol to achieve desired reaction products. In the synthesis of (−)-cladiella-6,11-dien-3-ol, a strained trisubstituted olefin was dihydroxylated diasetereoselectively with N-methylmorpholine N-oxide (NMO) and osmium tetroxide, in the presence of an unstrained olefin. En route to (±)-periplanone B, chemists achieved a facial selective epoxidation of an enone intermediate using tert-butyl hydroperoxide in the presence of two other alkenes. Sodium borohydride reduction of a 10-membered ring enone intermediate en route to the sesquiterpene eucannabinolide proceeded as predicted by molecular modelling calculations that accounted for the lowest energy macrocycle conformation. Substrate-controlled synthetic schemes have many advantages, since they do not require the use of complex asymmetric reagents to achieve selective transformations. Reagent control: addition of chiral allylmetals to achiral aldehydes In organic synthesis, reagent control is an approach to selectively forming one stereoisomer out of many, the stereoselectivity is determined by the structure and chirality of the reagent used. When chiral allylmetals are used for nucleophilic addition reaction to achiral aldehydes, the chirality of the newly generated alcohol carbon is determined by the chirality of the allymetal reagents (Figure 1). The chirality of the allymetals usually comes from the asymmetric ligands used. The metals in the allylmetal reagents include boron, tin, titanium, silicon, etc. Various chiral ligands have been developed to prepare chiral allylmetals for the reaction with aldehydes. H. C. Brown was the first to report the chiral allylboron reagents for asymmetric allylation reactions with aldehydes. The chiral allylboron reagents were synthesized from the natural product (+)-a-pinene in two steps. The TADDOL ligands developed by Dieter Seebach has been used to prepare chiral allyltitanium compounds for asymmetric allylation with aldehydes. Jim Leighton has developed chiral allysilicon compounds in which the release of ring strain facilitated the stereoselective allylation reaction, 95% to 98% enantiomeric excess could be achieved for a range of achiral aldehydes. See also Macrocyclic stereocontrol Cieplak effect References External links The Evolution of Models for Carbonyl Addition Evans Group Afternoon Seminar Sarah Siska February 9, 2001 Stereochemistry Induct