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Stereodivergent Synthesis of Highly Substituted Tetrahydropyrans
Author(s) -
Schneider Christoph,
Schuffenhauer Ansgar
Publication year - 2000
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(200001)2000:1<73::aid-ejoc73>3.0.co;2-4
Subject(s) - enantiopure drug , chemistry , stereoselectivity , intramolecular force , conjugate , combinatorial chemistry , stereochemistry , derivative (finance) , enantioselective synthesis , organic chemistry , catalysis , mathematical analysis , mathematics , financial economics , economics
Intramolecular oxa‐conjugate addition has been employed in a stereoselective synthesis of enantiopure polyalkyl‐substituted tetrahydropyrans, which are frequently found as substructures in many natural products. The requisite cyclization precursors, 7‐hydroxy‐2‐enimides 3 and 7‐hydroxy‐2‐enoates 6 were easily accessible by silyloxy Cope rearrangements of the appropriate chiral syn ‐aldols. It was found that the stereoselectivity of the cyclization could be controlled by judicious choice of the carboxylic acid derivative, resulting in a kinetically controlled reaction for the imides and a thermodynamically controlled process for the esters. Mechanistic considerations that could account for the stereocontrol of the process are outlined.