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Synfacts 2021; 17(09): 1019
DOI: 10.1055/s-0040-1720802
Metals in Synthesis

The Hosomi–Sakurai Reaction

Contributor(s):
Mark Lautens
,
Austin D. Marchese
Hosomi A, Sakurai H. * Tohoko University, Sendai, Japan
Syntheses of γ,δ-Unsaturated Alcohols from Allylsilanes and Carbonyl Compounds in the Presence of Titanium Tetrachloride.

Tetrahedron Lett. 1976;
17: 1295-1298
DOI: 10.1016/S0040-4039(00)78044-0.
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Key words

titanium catalysis - Lewis acids - allylation - organosilicon - carbonyl groups

Significance

The Hosomi–Sakurai reaction is a powerful synthetic tool used to add a nucleophilic allyl group to ketones and aldehydes under Lewis-acidic conditions. In this original 1976 report of the reaction, Hosomi and Sakurai illustrate a truly remarkable scope, adding allyltrimethylsilane to a variety of carbonyl-containing compounds, using only TiCl4, with reaction times typically being under ten minutes. The reaction typically worked best with alkyl-derived aldehydes, though ketones and benzaldehyde were amenable to the reaction. In the case of benzaldehyde, BF3·OEt2 was used as the Lewis acid.


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Comment

The Hosomi–Sakurai reaction initiates by coordination of the oxaphilic Lewis acid to the carbonyl group. Subsequent attack of the olefin forms a silyl-stabilized secondary β-cation. A nucleophilic source of halogen then attacks the TMS group, thereby generating a double bond. Since this report, a wide variety of catalytic and enantio­selective variants of this reaction have been discovered (see Review below).


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Review

J. J. Lade, S. D. Pardeshi, K. S. Vadagaonkar, K. Murugan, A. C. Chaskar RSC Adv. 2017, 7, 8011–8033.


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Publication History

Article published online:
18 August 2021

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