Home
Resources
Publications
Acetyltrimethylsilane, Trifluoromethyltrimethylsilane, and Prenyl Esters: A Three-Component System for the Synthesis of Gem-Difluoroanalogues of Monoterpenes

Acetyltrimethylsilane, Trifluoromethyltrimethylsilane, and Prenyl Esters: A Three-Component System for the Synthesis of Gem-Difluoroanalogues of Monoterpenes

O Lefebvre, T Brigaud, C Portella

J Org Chem. 2001 Jun 15;66(12):4348-51.

PMID: 11397175

Abstract:

The preparation of 3,3-difluoro-6-methylhept-5-en-2-one 1, a key intermediate for the synthesis of 4,4-difluoroterpenes, and applications in linalool and geraniol series are described. The process involves 1,1-difluoro-2-trimethylsilyoxypropene, an enol silyl ether prepared from acetyltrimethylsilane and trifluoromethyltrimethylsilane, and its reaction in situ with prenyl benzoate, under catalysis by trimethylsilyl trifluoromethanesulfonate. Optimized conditions leading to either the desired enol silyl ether or the unprecedented methyl(trifluoromethyl)trimethylsilyl carbinol 4 have been achieved. The prenylation of the enol silyl ether gives a 9/1 mixture of regioisomers, in favor of the expected ketone 1. Treatment of 1 with vinylmagnesium bromide leads to (+/-)-4,4-difluorolinalool 7. Reaction with the lithium enolate of ethyl diethylphosphonoacetate, and then LAH reduction, converts 1 to 4,4-difluorogeraniol 11, with complete stereoselectivity.

Chemicals Related in the Paper:

Catalog Number	Product Name	Structure	CAS Number	Price
AP13411488	Acetyltrimethylsilane		13411-48-8	Price

As a specialist in analytical chemical Products, Alfa Chemistry offers consumers a wealth of raw materials and a full range of technologies and services.

QUICK LINKS

HEADQUARTERS

Tel:

Fax:

Email: