Stereoselective C-glycosylation reactions of ribose derivatives

Electronic effects of five-membered ring oxocarbenium ions

Catharine H. Larsen, Brian H. Ridgway, Jared T. Shaw, Deborah M. Smith, Keith Woerpel

Research output: Contribution to journalArticle

Abstract

The factors controlling the highly α-selective C-glycosylation of ribose derivatives were determined by examining the Stereoselective reactions of 18 ribose analogues differing in substitution at C-2, C-3, and C-4. The lowest energy conformers of the intermediate oxocarbenium ions display the C-3 alkoxy group in a pseudoaxial orientation to maximize electrostatic effects. To a lesser extent, the C-2 substituent prefers a pseudoequatorial position, and the alkyl group at C-4 has little influence on conformational preferences. In all cases, the product was formed by stereoelectronically preferred inside attack on the lowest energy conformer.

Original languageEnglish (US)
Pages (from-to)10879-10884
Number of pages6
JournalJournal of the American Chemical Society
Volume127
Issue number31
DOIs
StatePublished - Aug 10 2005

Fingerprint

Glycosylation
Ribose
Electrostatics
Substitution reactions
Ions
Derivatives
Static Electricity
alkoxyl radical

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Stereoselective C-glycosylation reactions of ribose derivatives : Electronic effects of five-membered ring oxocarbenium ions. / Larsen, Catharine H.; Ridgway, Brian H.; Shaw, Jared T.; Smith, Deborah M.; Woerpel, Keith.

In: Journal of the American Chemical Society, Vol. 127, No. 31, 10.08.2005, p. 10879-10884.

Research output: Contribution to journalArticle

Larsen, Catharine H. ; Ridgway, Brian H. ; Shaw, Jared T. ; Smith, Deborah M. ; Woerpel, Keith. / Stereoselective C-glycosylation reactions of ribose derivatives : Electronic effects of five-membered ring oxocarbenium ions. In: Journal of the American Chemical Society. 2005 ; Vol. 127, No. 31. pp. 10879-10884.
@article{dc60e21898c84dcc93062d9d722e9e17,
title = "Stereoselective C-glycosylation reactions of ribose derivatives: Electronic effects of five-membered ring oxocarbenium ions",
abstract = "The factors controlling the highly α-selective C-glycosylation of ribose derivatives were determined by examining the Stereoselective reactions of 18 ribose analogues differing in substitution at C-2, C-3, and C-4. The lowest energy conformers of the intermediate oxocarbenium ions display the C-3 alkoxy group in a pseudoaxial orientation to maximize electrostatic effects. To a lesser extent, the C-2 substituent prefers a pseudoequatorial position, and the alkyl group at C-4 has little influence on conformational preferences. In all cases, the product was formed by stereoelectronically preferred inside attack on the lowest energy conformer.",
author = "Larsen, {Catharine H.} and Ridgway, {Brian H.} and Shaw, {Jared T.} and Smith, {Deborah M.} and Keith Woerpel",
year = "2005",
month = "8",
day = "10",
doi = "10.1021/ja0524043",
language = "English (US)",
volume = "127",
pages = "10879--10884",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "31",

}

TY - JOUR

T1 - Stereoselective C-glycosylation reactions of ribose derivatives

T2 - Electronic effects of five-membered ring oxocarbenium ions

AU - Larsen, Catharine H.

AU - Ridgway, Brian H.

AU - Shaw, Jared T.

AU - Smith, Deborah M.

AU - Woerpel, Keith

PY - 2005/8/10

Y1 - 2005/8/10

N2 - The factors controlling the highly α-selective C-glycosylation of ribose derivatives were determined by examining the Stereoselective reactions of 18 ribose analogues differing in substitution at C-2, C-3, and C-4. The lowest energy conformers of the intermediate oxocarbenium ions display the C-3 alkoxy group in a pseudoaxial orientation to maximize electrostatic effects. To a lesser extent, the C-2 substituent prefers a pseudoequatorial position, and the alkyl group at C-4 has little influence on conformational preferences. In all cases, the product was formed by stereoelectronically preferred inside attack on the lowest energy conformer.

AB - The factors controlling the highly α-selective C-glycosylation of ribose derivatives were determined by examining the Stereoselective reactions of 18 ribose analogues differing in substitution at C-2, C-3, and C-4. The lowest energy conformers of the intermediate oxocarbenium ions display the C-3 alkoxy group in a pseudoaxial orientation to maximize electrostatic effects. To a lesser extent, the C-2 substituent prefers a pseudoequatorial position, and the alkyl group at C-4 has little influence on conformational preferences. In all cases, the product was formed by stereoelectronically preferred inside attack on the lowest energy conformer.

UR - http://www.scopus.com/inward/record.url?scp=23744510729&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=23744510729&partnerID=8YFLogxK

U2 - 10.1021/ja0524043

DO - 10.1021/ja0524043

M3 - Article

VL - 127

SP - 10879

EP - 10884

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 31

ER -