Stereodivergent Synthesis of Functionalized Tetrahydropyrans Accelerated by Mechanism-Based Allylboration and Bioinspired Oxa-Michael Cyclization

A stereodivergent strategy enabled by bioinspired oxa‐Michael cyclization was developed for the synthesis of functionalized tetrahydropyrans on the basis of the inherent symmetry in 1,3‐diols, the symmetries of which were tunable by stereoselective hydroboration of an allene with a variety of alkylb...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2016-05, Vol.55 (21), p.6280-6284
Main Authors: Yang, Lin, Lin, Zuming, Huang, Sha-Hua, Hong, Ran
Format: Article
Language:English
Subjects:
Allene
allenes
Allyl compounds
boranes
Chemical reactions
Diols
heterocycles
homoallylic alcohols
Hydroboration
Michael addition
Reagents
Synthesis
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Summary:A stereodivergent strategy enabled by bioinspired oxa‐Michael cyclization was developed for the synthesis of functionalized tetrahydropyrans on the basis of the inherent symmetry in 1,3‐diols, the symmetries of which were tunable by stereoselective hydroboration of an allene with a variety of alkylborane reagents and subsequent allylation of an aldehyde. The mechanism‐based utilization of monoalkyl borane in the hydroboration and allylation cascade is unprecedented. Symmetry breakdown: The thermodynamic and kinetic hydroboration of allenes and subsequent allylboration provide a key stereodefinable module with a latent symmetry. Following a deprotection/chain elongation/oxa‐Michael cyclization sequence, the stereocogeners of highly functionalized tetrahydropyrans were synthesized for rapid access to structural motifs found in bioactive polyketides.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201600558