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Pheromone Synthesis, CLVIII. New Synthesis and Revision of the Absolute Configuration of the Hemiacetal Pheromone of the Spined Citrus Bug Biprorulus bibax
Author(s) -
Mori Kenji,
Amaike Masayasu,
Watanabe Hidenori
Publication year - 1993
Publication title -
liebigs annalen der chemie
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 0170-2041
DOI - 10.1002/jlac.1993199301210
Subject(s) - chemistry , hemiacetal , absolute configuration , stereochemistry , enantioselective synthesis , pheromone , claisen rearrangement , enantiomer , lactone , hydrolysis , lipase , optically active , total synthesis , organic chemistry , catalysis , enzyme , botany , biology
The enantiomers and the racemate of (3 R ,4 S ,1′ E )‐3,4‐bis(1′‐butenyl)tetrahydro‐2‐furanol ( 1 ) were synthesized by employing Ireland's ester enolate Claisen rearrangement of 5 as the key reaction to provide the corresponding lactone 3 via 4 . Optically active 3 was prepared by employing either chemical asymmetric reduction [ 12 → ( S )‐ 8b ] or lipase‐mediated asymmetric hydrolysis ( 9 → 10 ) and acetylation ( meso ‐ 2 → ent ‐ 10 ) as the key transformations. The absolute configuration of the naturally occurring 1 was revised as (3 R ,4 S ) on the basis of the chemical asymmetric synthesis of (3 S ,4 R )‐ 3 by starting from ( S )‐ 8b of known stereochemistry.