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Title: Highly Selective Supramolecular Catalyzed Allylic AlcoholIsomerization

Abstract

No abstract prepared.

Authors:
; ;
Publication Date:
Research Org.:
Ernest Orlando Lawrence Berkeley NationalLaboratory, Berkeley, CA (US)
Sponsoring Org.:
USDOE Director. Office of Science. Basic EnergySciences
OSTI Identifier:
923458
Report Number(s):
LBNL-62066
Journal ID: ISSN 0002-7863; JACSAT; R&D Project: 402103; BnR: KC0302010; TRN: US200804%%1168
DOE Contract Number:
DE-AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 129; Related Information: Journal Publication Date: 02/16/2007
Country of Publication:
United States
Language:
English
Subject:
37; ALCOHOLS; ISOMERIZATION; CHEMISTRY

Citation Formats

Leung, Dennis H., Bergman, Robert G., and Raymond, Kenneth N.. Highly Selective Supramolecular Catalyzed Allylic AlcoholIsomerization. United States: N. p., 2006. Web.
Leung, Dennis H., Bergman, Robert G., & Raymond, Kenneth N.. Highly Selective Supramolecular Catalyzed Allylic AlcoholIsomerization. United States.
Leung, Dennis H., Bergman, Robert G., and Raymond, Kenneth N.. Wed . "Highly Selective Supramolecular Catalyzed Allylic AlcoholIsomerization". United States. doi:.
@article{osti_923458,
title = {Highly Selective Supramolecular Catalyzed Allylic AlcoholIsomerization},
author = {Leung, Dennis H. and Bergman, Robert G. and Raymond, Kenneth N.},
abstractNote = {No abstract prepared.},
doi = {},
journal = {Journal of the American Chemical Society},
number = ,
volume = 129,
place = {United States},
year = {Wed Dec 27 00:00:00 EST 2006},
month = {Wed Dec 27 00:00:00 EST 2006}
}
  • Ethynylcarbinols upon heating with polyvanadium organosiloxanes and other esters of vanadic acid isomerize to unsaturated aldehydes, while 1-alkenylcarbinols under the same conditions undergo allylic rearrangement. The authors have studied the rearrangement of these carbinols capable of reacting by both pathways and thus serving as models for a study of intramolecular competition between these two type of processes. In the presence of polyvanadium organosiloxane, the carbinols undergo virtually complete isomerization to 2-hydroxy-3-alken-5-ynes. In other words, the allylic rearrangement predominates. No significant amounts of sorbinaldehydes, which would be formed as the products of the other reaction, were detected. An analysis of themore » NMR spectra is given.« less
  • The reactions of N-methyl-, N-phenyl-, N-amyl-, and N-allyl-p-toluenesulfonamides and the corresponding butanesulfonamides and also of unsubstituted p-toluenesulfonamide with allyl alcohols, ethers, esters, amines, sulfides, and sulfones, catalyzed by the low-valence compounds of palladium nickel, iron, cobalt, zirconium, chromium, and copper and leading to difficultly obtainable N-alkenylsulfonamides with specific structures, were investigated. The complex catalysts based on compounds of nickel, iron, and copper activated with triphenylphosphine direct the reaction of N-methyltoluenesulfonamide with 2,7-octadienyl acetate toward the exclusive formation of N-methyl-N-(1,7-octadiene-3-yl)-p-toluenesulfonamide, while the phosphine complexes of palladium direct the reaction toward N-methyl-N-(2,7-octadienyl)-p-toluenesulfonamide. The ..pi..-allyl complexes of palladium, containing the sulfonamide molecules inmore » the coordination sphere of the central atom of the catalyst, promote the isomerization of 2,7-octadienyl acetate to the branched 1,7-isomer.« less
  • The ruthenium complex ({eta}{sup 5}-C{sub 5}H{sub 5})(PPh{sub 3}){sub 2}RuCl (1) catalyzes the addition of allytic alcohols to terminal alkynes, yielding {Beta}{gamma}-unsaturated ketones. The intermediacy of a ruthenium vinylidene complex is indicated by the synthesis of this proposed intermediate and the demonstration of the same reaction profile as with catalyst 1. Loss of terminal deuterium in labeled alkynes supports this conclusion. Ligand substitution studies demonstrate the necessity of phosphine loss and precoordination of the allylic alcohol. Deuterium labeling of allyl alcohol demonstrates that the two allylic termini do not become equivalent and that the olefin geometry does not scramble. In contrastmore » to these observations, 3-buten-2-ol shows complete regioselectivity in the condensation but randomization of olefin geometry as determined by deuterium labeling. A cohesive mechanistic rationale accommodates these seemingly disparate observations. 24 refs., 4 figs.« less