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. 2019 Jul 8;58(28):9542-9546.
doi: 10.1002/anie.201903587. Epub 2019 May 30.

S-Adamantyl Group Directed Site-Selective Acylation: Applications in Streamlined Assembly of Oligosaccharides

Stephanie A Blaszczyk  1   2 , Guozhi Xiao  1 , Peng Wen  1 , Hua Hao  3 , Jessica Wu  1 , Bo Wang  1 , Francisco Carattino  3 , Ziyuan Li  1 , Daniel A Glazier  2 , Bethany J McCarty  2 , Peng Liu  3 , Weiping Tang  1   2
Affiliations

S-Adamantyl Group Directed Site-Selective Acylation: Applications in Streamlined Assembly of Oligosaccharides

Stephanie A Blaszczyk et al. Angew Chem Int Ed Engl. .

Abstract

The site-selective functionalization of carbohydrates is an active area of research. Reported here is the surprising observation that the sterically encumbered adamantyl group directed site-selective acylation at the C2 position of S-glycosides through dispersion interactions between the adamantyl C-H bonds and the π system of the cationic acylated catalyst, which may have broad implications in many other chemical reactions. Because of their stability, chemical orthogonality, and ease of activation for glycosylation, the site-selective acylation of S-glycosides streamlines oligosaccharide synthesis and will have wide applications in complex carbohydrate synthesis.

Keywords: acylation; carbohydrates; glycosylation; noncovalent interactions; synthetic methods.

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Figures

Figure 1.
Figure 1.
Most stable transition states of the C2- and C3-acylation of S-glycoside 6e.
Scheme 1:
Scheme 1:
Site-selective acylation of O- and S-glycosides.
Scheme 2:
Scheme 2:
Comparison of the relative strength of a cation-lone pair and dispersion interactions. a) Conditions: (R)-BTM (10 mol %), isobutyric anhydride (2.5 eq), iPr2NEt (3.0 eq), CHCl3, rt, Ar
Scheme 3.
Scheme 3.
Comparison of method efficiency to prepare oligosaccharides using either cation-n directed C2 OH acylation with O-glycosides or site-selective acylation using readily activated S-glycosides. Reaction conditions: a) (R)-BTM, LevOH, Piv2O, iPr2Et, CHCl3, rt, 85%; b) 32, TMSOTf, CH2Cl2, 0°C-rt, 83%; (c) CAN, CH3CN, H2O, 70%; d) CCl3CN, DBU, 64%; (e) 29e, TMSOTf, CH2Cl2, 0°C-rt, 81%; f) (R)-BTM, LevOH, Piv2O, iPr2Et, CHCl3, rt, 88%; g) 32, TMSOTf, CH2Cl2, 0°C-rt, 62%; (h) 29e, NIS, TMSOTf, CH2Cl2:CH3CN (2:1), −78°C–0°C, 69%
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