Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination.

Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Research Abstract Details 

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Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Abstract Text:

Thomas M Weathers,Yuanhua Wang,Michael P Doyle,

The use of catalytic metal carbene methodology with diazoacetates for the construction in high yield of polyether macrocycles having ring sizes greater than 25 has been achieved by preventing access to gamma-C-H positions for intramolecular insertion. Cyclopropanation is the exclusive outcome of reactions performed with dirhodium(II) catalysts, and product yields of greater than 70% are obtained without resorting to high dilution with solvents. With copper(I) catalysts having multiple sites for polyether coordination, intramolecular oxonium ylide formation occurs at the terminal oxygen, followed by [2,3]-sigmatropic rearrangement of the pendant allyl group, in competition with cyclopropanation. Sodium ion coordination with the reactant diazo compound inhibits oxonium ylide formation in copper-catalyzed reactions. The composite results are consistent with copper serving as a template for the substrate as well as the site in the ether complex for diazo decomposition and subsequent metal carbene reactions.

Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Publishing Authors By Initials

TM Weathers,Y Wang,MP Doyle,

For similar polycyclic compounds: macrocyclic compounds research abstracts see: polycyclic compounds: macrocyclic compounds research

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Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Journal Published:

PUBLICATION TYPE: Research Support, U.S. Gov't,

Journal: The Journal of organic chemistry

VOLUME: 71

Page Numbers: 8183-9

Journal Abbreviation: J. Org. Chem.

ISSN: 0022-3263

DAY: 13

MONTH: Oct

YEAR: 2006

Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Information

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LANGUAGE: eng

NlmUniqueID: 2985193

Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Keywords Mesh Terms:

KEYWORDS: Macrocyclic Compounds

MESH TERMS: chemical synthesis

Chemical & Substance for Abstract: Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination. Information

Substance Name: Macrocyclic Compounds

Registry Number: 0

Grant and Affiliation Information for Polyether macrocycles from intramolecular cyclopropanation and ylide formation. Effect of catalyst and coordination.

AFFILIATION: Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA.

Country: United States

AGENCY: United States NIGMS

GRANT: GM 46503

ACRONYM: GM

MEDLINETA: J Org Chem

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