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Application of the Silyloxy Cope Rearrangement of Chiral Aldol Products Towards a Synthesis of (+)‐Lasiol
Author(s) -
Schneider Christoph
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199808)1998:8<1661::aid-ejoc1661>3.0.co;2-0
Subject(s) - stereocenter , aldol reaction , chemistry , natural product , total synthesis , stereochemistry , stereoselectivity , cope rearrangement , wittig reaction , protecting group , bond cleavage , methyl group , organic chemistry , enantioselective synthesis , group (periodic table) , catalysis , alkyl
A stereoselective total synthesis of the natural product (+)‐lasiol ( 1 ) has been achieved. The key step of our synthesis is a silyloxy‐Cope rearrangement of the chiral, silylated aldol product 2 which proceeds selectively through the chair‐like transition state with the silyloxy group in the pseudoaxial and the carboximide group in the pseudoequatorial position. The two methyl‐substituted stereogenic centers of the natural product are generated with ds > 97:3. The rearrangement product 4 is converted to the natural product via a Wittig olefination reaction and an oxidative cleavage of a double bond, respectively.