Abstract
This thesis, divided into three parts, is concerned with the application of camphor-derived chiral β-amino alcohol or β-amino thiol in catalytic asymmetric conjugate addition of carbon nucleophiles to α,β-unsaturated systems and asymmetric addition reactions of organozinc to carbonyl compounds. The first part has discuss the complex of (+)-MINBOL 28 and Ni(acac)2 (12.5 mol% and 0.5 mol% respectively) catalyzes enantioselective conjugate 1,4-addition of dialkylzinc to α,β-unsaturated enones in propionitrile, giving the corresponding chiral Michael adducts in high enantioselectivities (up to 93% ee) and good yields without extra addition of any coligand. The second part is to develop new camphor-derived (2S,4R)-4- hydroxy-L-prolinamide 58 as organocatalyst, which is capable of catalyzing Michael addition reaction of isobutyraldehyde and nitrostyrenes. By using 20 mol% catalytic loading of organocatalyst 58 and 5.0 eq. of water without additional additive at room temperature gave chiral Michael adduct with up to 92% ee and excellent yield. Furthermore, the conjugate addition of α-substituted aldehyde to trans-β-nitrostyrene in the presence of 5.0 eq. of CHCl3 proceeded with high diastereoselectivit- ies (up to syn/anti of 98:2) and enantioselectivities (79□88 % ee). The third part applied (-)-(1S,2R)-10-(N,N-diisopropylsulfonamido)-2- morpholin-4-ylmethyl-thiaisoborneol [(-)-SMOTIB 66] as chiral ligand (10 mol% loading) in the catalytic asymmetric addition of alkynylzinc to aromatic aldehyde to build chiral propargylic alcohols skeleton in good enantioselectivities (up to 92% ee) and yields (up to 97%).