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Total Synthesis of Rishirilide B by Organocatalytic Oxidative Kinetic Resolution: Revision of Absolute Configuration of (+)‐Rishirilide B
Author(s) -
Odagi Minami,
Furukori Kota,
Takayama Kan,
Noguchi Keiichi,
Nagasawa Kazuo
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201701431
Subject(s) - kinetic resolution , chemistry , absolute configuration , regioselectivity , hydroxylation , enantioselective synthesis , guanidine , bifunctional , stereochemistry , isomerization , total synthesis , tetralones , oxidative phosphorylation , organic chemistry , catalysis , enzyme , biochemistry
Described herein is the enantioselective syntheses of (+)‐ and (−)‐rishirilide B from the corresponding optically active β‐substituted tetralones, which were obtained by oxidative kinetic resolution based on α‐hydroxylation in the presence of a chiral guanidine‐bisurea bifunctional organocatalyst. Benzylic oxidation of the tetralones at C1 followed by regioselective isomerization of the oxabenzonorbornadiene structure led to rishirilide B. Our findings lead to the revision of the previously proposed (2R,3R,4R) absolute configuration of (+)‐rishirilide B to (2S,3S,4S).