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. 2013 Mar 4;19(10):3437-44.
doi: 10.1002/chem.201203987. Epub 2013 Jan 24.

The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex

Paramita Mukherjee  1 , Ross A Widenhoefer
Affiliations

The regio- and stereospecific intermolecular dehydrative alkoxylation of allylic alcohols catalyzed by a gold(I) N-heterocyclic carbene complex

Paramita Mukherjee et al. Chemistry. .

Abstract

A 1:1 mixture of [AuCl(IPr)] (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidine) and AgClO(4) catalyzes the intermolecular dehydrative alkoxylation of primary and secondary allylic alcohols with aliphatic primary and secondary alcohols to form allylic ethers. These transformations are regio- and stereospecific with preferential addition of the alcohol nucleophile at the γ-position of the allylic alcohol syn to the departing hydroxyl group and with predominant formation of the E stereoisomer. The minor α regioisomer is formed predominantly through a secondary reaction manifold involving regioselective γ-alkoxylation of the initially formed allylic ether rather than by the direct α-alkoxylation of the allylic alcohol.

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Figures

Figure 1
Figure 1
Concentration versus time plot for the reaction of a 1:4 mixture of trans-4-hexen-3-ol (◊) with 4-methylbenzyl alcohol catalyzed by a 1:1 mixture of (IPr)AuCl and AgClO4 (5 mol %) in CD2Cl2 at room temperature to form 4 (□) and 5 (Δ).
Scheme 1
Scheme 1
Gold-catalyzed alkoxylation of trans-2-buten-1-ol with 4-methylbenzyl alcohol.
Scheme 2
Scheme 2
Gold-catalyzed alkoxylation of allylic ether 7a with benzyl alcohol.
Scheme 3
Scheme 3
Minor regioisomer 5 is formed primarily via secondary γ-alkoxylation of 4 and not through direct α-alkoxylation of trans-3-penten-2-ol.
Scheme 4
Scheme 4
Stereochemical analysis of the gold-catalyzed reaction of (R,E)-11 with n-butanol.
Scheme 5
Scheme 5
Stereochemical analysis of the gold-catalyzed reaction of (R,Z)-11 with n-butanol.
Scheme 6
Scheme 6
Regio- and stereochemical outcomes of the triflic acid catalyzed intermolecular alkoxylation of (R,E)-11.
Scheme 7
Scheme 7
Regio- and stereochemical outcomes of the BF3·OEt2 catalyzed intermolecular alkoxylation of (R,E)-11.
Scheme 8
Scheme 8
Proposed mechanism for the gold-catalyzed γ-regioselective and syn-stereoselective alkoxylation of (R,E)-11 and (R,Z)-11.
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