Abstract
Acyclic stereoselection based on the stereoselective ketone reduction and its application to natural products synthesis are reviewed. 1) Highly stereoselective reductions of α-methyl-β-keto ester, α-methyl-β-hydroxy ketone, α, β-epoxy ketone, and α-hydroxy ketone with Zn (BH4)2 and α-silyloxy ketone with NaAlH2 (OCH2CH2OMe)2 are described. The relation between substitution pattern of ketone and stereoselectivity of the reduction are extensively studied. 2) Highly stereocontrolled method for the synthesis of 1, 3-syn and anti-polyols has been developed based on the stereoselective reduction of six-membered β-keto acetal and successive transthioacetalization. 3) The new methods developed in 1) and 2) have been successfully applied for the synthesis of natural products or related compounds : erythronolide A seco-acid derivative (43), oudemansin (46), antimycin A3 (47), blastmycinone (48), four synthons having three consecutive chiral centers (69-72), bicyclic acetal (75), and pederin (76).
