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. 2019 Mar 1;84(5):2415-2424.
doi: 10.1021/acs.joc.8b02613. Epub 2019 Feb 15.

Substrate-Controlled Direct α-Stereoselective Synthesis of Deoxyglycosides from Glycals Using B(C6F5)3 as Catalyst

Abhijit Sau  1 , Carlos Palo-Nieto  1 , M Carmen Galan  1
Affiliations

Substrate-Controlled Direct α-Stereoselective Synthesis of Deoxyglycosides from Glycals Using B(C6F5)3 as Catalyst

Abhijit Sau et al. J Org Chem. .

Abstract

B(C6F5)3 enables the metal-free unprecedented substrate-controlled direct α-stereoselective synthesis of deoxyglycosides from glycals. 2,3-Unsaturated α- O-glycoside products are obtained with deactivated glycals at 75 °C in the presence of the catalyst, while 2-deoxyglycosides are formed using activated glycals that bear no leaving group at C-3 at lower temperatures. The reaction proceeds in good to excellent yields via concomitant borane activation of glycal donor and nucleophile acceptor. The method is exemplified with the synthesis of a series of rare and biologically relevant glycoside analogues.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. BCF-Catalysed Synthesis of 2,3-Unsaturated Glycosides from “Disarmed” Glycals (Pathway A) and 2-α-Deoxyglycosides from “armed” Glycals (Pathway B)
Scheme 2
Scheme 2. Reaction of Glycals 1a–1e, with Glycosyide Acceptors 2e
Scheme 3
Scheme 3. Synthesis of Rare Glycosides 6–8
Scheme 4
Scheme 4. Model Glycosylations of 2a or 17 with Glycal Donors 15, 1a, or 9a
Scheme 5
Scheme 5. Proposed Mechanism
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