A new mechanistic proposal for the origin of α-homoallylic alcohols in indium-mediated allylation reactions in water

Teck Peng Loh; Kui Thong Tan; Qi Ying Hu

doi:10.1016/S0040-4039(01)01884-6

A new mechanistic proposal for the origin of α-homoallylic alcohols in indium-mediated allylation reactions in water

Teck Peng Loh^*, Kui Thong Tan, Qi Ying Hu

^*Corresponding author for this work

National University of Singapore

Research output: Contribution to journal › Article › peer-review

50 Citations (Scopus)

Abstract

A new mechanism is proposed for the α-regioselective indium-mediated allylation reaction in water. Based on the results and observations obtained from an NMR study, a cross-over experiment and the complete inversion of the stereochemistry of 22β γ-adduct homoallylic sterols to the 22α α-adduct homoallylic sterols, it is suggested that the initially formed γ-adduct undergoes a bond cleavage to generate the parent aldehyde in situ followed by a concerted rearrangement, perhaps a retro-ene reaction followed by a 2-oxonia [3,3]-sigmatropic rearrangement to furnish the α-adduct.

Original language	English
Pages (from-to)	8705-8708
Number of pages	4
Journal	Tetrahedron Letters
Volume	42
Issue number	49
DOIs	https://doi.org/10.1016/S0040-4039(01)01884-6
Publication status	Published - Dec 3 2001
Externally published	Yes

ASJC Scopus Subject Areas

Biochemistry
Drug Discovery
Organic Chemistry

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abstract = "A new mechanism is proposed for the α-regioselective indium-mediated allylation reaction in water. Based on the results and observations obtained from an NMR study, a cross-over experiment and the complete inversion of the stereochemistry of 22β γ-adduct homoallylic sterols to the 22α α-adduct homoallylic sterols, it is suggested that the initially formed γ-adduct undergoes a bond cleavage to generate the parent aldehyde in situ followed by a concerted rearrangement, perhaps a retro-ene reaction followed by a 2-oxonia [3,3]-sigmatropic rearrangement to furnish the α-adduct.",

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AU - Loh, Teck Peng

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AU - Hu, Qi Ying

PY - 2001/12/3

Y1 - 2001/12/3

N2 - A new mechanism is proposed for the α-regioselective indium-mediated allylation reaction in water. Based on the results and observations obtained from an NMR study, a cross-over experiment and the complete inversion of the stereochemistry of 22β γ-adduct homoallylic sterols to the 22α α-adduct homoallylic sterols, it is suggested that the initially formed γ-adduct undergoes a bond cleavage to generate the parent aldehyde in situ followed by a concerted rearrangement, perhaps a retro-ene reaction followed by a 2-oxonia [3,3]-sigmatropic rearrangement to furnish the α-adduct.

AB - A new mechanism is proposed for the α-regioselective indium-mediated allylation reaction in water. Based on the results and observations obtained from an NMR study, a cross-over experiment and the complete inversion of the stereochemistry of 22β γ-adduct homoallylic sterols to the 22α α-adduct homoallylic sterols, it is suggested that the initially formed γ-adduct undergoes a bond cleavage to generate the parent aldehyde in situ followed by a concerted rearrangement, perhaps a retro-ene reaction followed by a 2-oxonia [3,3]-sigmatropic rearrangement to furnish the α-adduct.

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A new mechanistic proposal for the origin of α-homoallylic alcohols in indium-mediated allylation reactions in water

Abstract

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