Selective reductions. 59. Effective intramolecular asymmetric reductions of alpha-, beta-, and gamma-keto acids with diisopinocampheylborane and intermolecular asymmetric reductions of the corresponding esters with B-chlorodiisopinocampheylborane.
A comparison of the stereochemistry of the products obtained from the intramolecular asymmetric reduction of a series of keto acids with (-)-diisopinocampheylborane and intermolecular asymmetric reduction of the corresponding series of keto esters with (-)-B-chlorodiisopinocampheylborane ((-)-DIP-Chloride) has been made. The stereochemistry of the hydroxy acids from the reduction of keto acids is dependent only on the enantiomer of the reagent used. The stereochemistry of the products from the reduction of keto esters is also consistent, except those of aliphatic alpha-keto esters. alpha-, beta-, and gamma-keto acids provide the corresponding hydroxy acids in 77-98% ee, and the alpha- and gamma- keto esters afford the hydroxy esters in 82->or=99% ee. beta-Keto esters do not undergo reduction. Although the reduction of delta-keto acids does not proceed under the same reaction conditions, the reduction of delta-keto esters is facile. All of the products from the reduction of gamma-keto acids and esters and delta-keto esters were converted to the corresponding lactones. This study revealed that DIP-Chloride is an efficient reagent for the reduction of alpha-keto esters at low temperatures.
Herbert C. Brown Center for Borane Research, Purdue University, West Lafayette, Indiana 47907-1393, USA. chandran@purdue.edu
P Veeraraghavan
PV
Ramachandran
Sangeeta
S
Pitre
Herbert C
HC
Brown