2-(trimethylsilylmethyl)allyl alcohol

Physical properties

bp 54–56 °C/2 mmHg; nD 20 1.454; d 0.861 g cm?3; fp 71?C.

Uses

2-Trimethylsilylmethyl-2-propen-1-ol reagent has been employed as a conjunctive reagent which is considered to be a synthetic equivalent of a zwitterionic, bifunctional compound possessing a nucleophilic allylic anion synthon and an electrophilic cation synthon in the same molecule. Derivatives function as trimethylenemethane (TMM) precursors and undergo cyclopentannulation reactions; methylenecyclopentanes; 2-acetoxymethyl-3-trimethylsilylpropene; [3+2] annulation; Methylenecyclopentane Annulation,Cyclocontraction-Spiroannulation, three-carbon condensative expansion; cyclocontraction–spiroannulation.

Preparation

2-Trimethylsilylmethyl-2-propen-1-ol is prepared in four steps from methallyl alcohol. The synthesis begins with the metalation with nbutyllithium (2 equiv) producing the dianion which is bissilylated by trapping with chlorotrimethylsilane to generate the allylsilane. The TMS ether is subsequently removed by hydrolysis (eq 1). The primary allylic alcohol serves as a precursor to more functionalized reagents.

Useful derivatives of the alcohol are the primary allylic chloride, mesylate, and acetate. These are easily prepared in a short number of steps as shown (eq 2) or by functionalization of the primary allylic alcohol.

Raw materials

Preparation Products