Stereoselectivity in the epoxidation of carbohydrate-based oxepines

Shankar D. Markad, Shijing Xia, Nicole L. Snyder, Bikash Surana, Martha D Morton, Christopher M. Hadad, Mark W. Peczuh

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

(Figure Presented) The facial selectivity in the DMDO epoxidation of carbohydrate-based oxepines derived from glucose, galactose, and mannose has been determined by product analysis and density functional theory (DFT, B3LYP/6-31+G**//B3LYP/6-31G*) calculations. Oxepines 3 and 4, derived from D-galactose and D-mannose, largely favor α- over β-epoxidation. The results reported here, along with selectivities in the DMDO-mediated epoxidation of D-xylose-based oxepine 1 and D-glucose-based oxepines 2 and 5 reported earlier, support a model in which electronic effects, guided by the stereochemistry of the oxygens on the oxepine ring, largely determine the stereoselectivity of epoxidation. Other contributing factors included conformational issues in the oxepine's transition state relative to the reactant, the asynchronicity in bond formation of the epoxide, and the overall steric bulk on the α- and β-faces of the oxepine. Considered together, these factors should generally predict facial selectivity in the DMDO-epoxidation of cyclic enol ethers.

Original languageEnglish (US)
Pages (from-to)6341-6354
Number of pages14
JournalJournal of Organic Chemistry
Volume73
Issue number16
DOIs
StatePublished - Aug 15 2008

Fingerprint

Oxepins
Stereoselectivity
Epoxidation
Carbohydrates
Mannose
Galactose
Glucose
Stereochemistry
Ethers
Xylose
Epoxy Compounds
Discrete Fourier transforms
Density functional theory
Byproducts
Oxygen

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Markad, S. D., Xia, S., Snyder, N. L., Surana, B., Morton, M. D., Hadad, C. M., & Peczuh, M. W. (2008). Stereoselectivity in the epoxidation of carbohydrate-based oxepines. Journal of Organic Chemistry, 73(16), 6341-6354. https://doi.org/10.1021/jo800979a

Stereoselectivity in the epoxidation of carbohydrate-based oxepines. / Markad, Shankar D.; Xia, Shijing; Snyder, Nicole L.; Surana, Bikash; Morton, Martha D; Hadad, Christopher M.; Peczuh, Mark W.

In: Journal of Organic Chemistry, Vol. 73, No. 16, 15.08.2008, p. 6341-6354.

Research output: Contribution to journalArticle

Markad, SD, Xia, S, Snyder, NL, Surana, B, Morton, MD, Hadad, CM & Peczuh, MW 2008, 'Stereoselectivity in the epoxidation of carbohydrate-based oxepines', Journal of Organic Chemistry, vol. 73, no. 16, pp. 6341-6354. https://doi.org/10.1021/jo800979a
Markad, Shankar D. ; Xia, Shijing ; Snyder, Nicole L. ; Surana, Bikash ; Morton, Martha D ; Hadad, Christopher M. ; Peczuh, Mark W. / Stereoselectivity in the epoxidation of carbohydrate-based oxepines. In: Journal of Organic Chemistry. 2008 ; Vol. 73, No. 16. pp. 6341-6354.
@article{eaf73bec2fc44533b68f3e1903902ab3,
title = "Stereoselectivity in the epoxidation of carbohydrate-based oxepines",
abstract = "(Figure Presented) The facial selectivity in the DMDO epoxidation of carbohydrate-based oxepines derived from glucose, galactose, and mannose has been determined by product analysis and density functional theory (DFT, B3LYP/6-31+G**//B3LYP/6-31G*) calculations. Oxepines 3 and 4, derived from D-galactose and D-mannose, largely favor α- over β-epoxidation. The results reported here, along with selectivities in the DMDO-mediated epoxidation of D-xylose-based oxepine 1 and D-glucose-based oxepines 2 and 5 reported earlier, support a model in which electronic effects, guided by the stereochemistry of the oxygens on the oxepine ring, largely determine the stereoselectivity of epoxidation. Other contributing factors included conformational issues in the oxepine's transition state relative to the reactant, the asynchronicity in bond formation of the epoxide, and the overall steric bulk on the α- and β-faces of the oxepine. Considered together, these factors should generally predict facial selectivity in the DMDO-epoxidation of cyclic enol ethers.",
author = "Markad, {Shankar D.} and Shijing Xia and Snyder, {Nicole L.} and Bikash Surana and Morton, {Martha D} and Hadad, {Christopher M.} and Peczuh, {Mark W.}",
year = "2008",
month = "8",
day = "15",
doi = "10.1021/jo800979a",
language = "English (US)",
volume = "73",
pages = "6341--6354",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "16",

}

TY - JOUR

T1 - Stereoselectivity in the epoxidation of carbohydrate-based oxepines

AU - Markad, Shankar D.

AU - Xia, Shijing

AU - Snyder, Nicole L.

AU - Surana, Bikash

AU - Morton, Martha D

AU - Hadad, Christopher M.

AU - Peczuh, Mark W.

PY - 2008/8/15

Y1 - 2008/8/15

N2 - (Figure Presented) The facial selectivity in the DMDO epoxidation of carbohydrate-based oxepines derived from glucose, galactose, and mannose has been determined by product analysis and density functional theory (DFT, B3LYP/6-31+G**//B3LYP/6-31G*) calculations. Oxepines 3 and 4, derived from D-galactose and D-mannose, largely favor α- over β-epoxidation. The results reported here, along with selectivities in the DMDO-mediated epoxidation of D-xylose-based oxepine 1 and D-glucose-based oxepines 2 and 5 reported earlier, support a model in which electronic effects, guided by the stereochemistry of the oxygens on the oxepine ring, largely determine the stereoselectivity of epoxidation. Other contributing factors included conformational issues in the oxepine's transition state relative to the reactant, the asynchronicity in bond formation of the epoxide, and the overall steric bulk on the α- and β-faces of the oxepine. Considered together, these factors should generally predict facial selectivity in the DMDO-epoxidation of cyclic enol ethers.

AB - (Figure Presented) The facial selectivity in the DMDO epoxidation of carbohydrate-based oxepines derived from glucose, galactose, and mannose has been determined by product analysis and density functional theory (DFT, B3LYP/6-31+G**//B3LYP/6-31G*) calculations. Oxepines 3 and 4, derived from D-galactose and D-mannose, largely favor α- over β-epoxidation. The results reported here, along with selectivities in the DMDO-mediated epoxidation of D-xylose-based oxepine 1 and D-glucose-based oxepines 2 and 5 reported earlier, support a model in which electronic effects, guided by the stereochemistry of the oxygens on the oxepine ring, largely determine the stereoselectivity of epoxidation. Other contributing factors included conformational issues in the oxepine's transition state relative to the reactant, the asynchronicity in bond formation of the epoxide, and the overall steric bulk on the α- and β-faces of the oxepine. Considered together, these factors should generally predict facial selectivity in the DMDO-epoxidation of cyclic enol ethers.

UR - http://www.scopus.com/inward/record.url?scp=50149103020&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=50149103020&partnerID=8YFLogxK

U2 - 10.1021/jo800979a

DO - 10.1021/jo800979a

M3 - Article

VL - 73

SP - 6341

EP - 6354

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 16

ER -