The Mitsunobu reaction of ortho-ethers of secondary benzylic alcohols. Concise enantioselective synthesis of a key intermediate of the novel β-adrenergic receptor antagonist MY336-a

Chiral secondary benzylic alcohols bearing an ortho-alkoxy substituent suffer ring-assisted racemization during the Mitsunobu reaction; however, their congeners bearing also a 3-substituent undergo virtually complete Mitsunobu inversion. A concise enantioselective synthesis of a key intermediate of...

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Bibliographic Details
Published inTetrahedron letters Vol. 37; no. 30; pp. 5329 - 5332
Main Author Kaufman, Teodoro S.
Format Journal Article
LanguageEnglish
Published OXFORD Elsevier Ltd 22.07.1996
Elsevier
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
(+)-4-DEMETHOXYDAUNOMYCIN
AZODICARBOXYLATE
STEREOCONVERGENT SYNTHESIS
MECHANISM
AMINES
ESTERIFICATION REACTION
STEREOSPECIFIC SYNTHESIS
AGENTS
TRIPHENYLPHOSPHINE
BORANE
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Summary:Chiral secondary benzylic alcohols bearing an ortho-alkoxy substituent suffer ring-assisted racemization during the Mitsunobu reaction; however, their congeners bearing also a 3-substituent undergo virtually complete Mitsunobu inversion. A concise enantioselective synthesis of a key intermediate of the β-adrenergic receptor antagonist MY336-a was achieved exploiting this observation. Virtually complete Mitsunobu inversion is achieved for R 1= Me, Bn when R 2= MeO. Partial racemization of the 4-nitrobenzoate ester (PNB) is observed when R= H. This allowed the enantioselective synthesis of 1.
ISSN:0040-4039
1873-3581
DOI:10.1016/0040-4039(96)01122-7