2-Trimethylsilylmethyl-2-propen

Trimethylsilylmethyl-2-propen-l-yl acetate. This important reagent is available from 2-chloro-2-propenol by reaction of the lithium alkoxide with MCjSiCH MgCl-(dppp)NiCl2, and acetylation of the product. 

Mercury(II) chloride, 175 Palladium(II) acetate, 232 Titanium(IV) chloride, 304 By [3 + 2] cycloaddition reactions 3-Acetoxy-2-trimethylsilylmethyl-l-propene, 3... 

Hydroxymethyl-3-allyltrimethylsilane. 2-(Trimethylsilylmethyl)-3 acetoxy-1 -propene. 2-(Trimethylsilyl)n]ethylallyl iodide. 

Trimethylsilyl-1,3-bis-(phenylseleno)propene, 60 Trimethylsilyl-5-chloro-l, 4-dienes, 49 Trimethylsilyldiazomethane, 573-574 2-Tnmethylsilylethanol, 4, 574 P (Trimethylsilyl)ethyllithium, 574-575 2-Trimethylsilylfuranes, 577 3 -Tnmethylsiiyl-4-hydroxy-1 -alkenes, 175 N-(TrimethyIsilyl)imidazole, 575 Trimethylsilyllithinm, 575 Trimethylsilylmethanethiol, 576 1 -Trimethylsilyl-1 -methoxyallene, 577 2-(Trimethylsilylmethyl)-3-acetoxy-1 -propene, 578-579... 

Palladium catalyzed [3+2j-cycloadditions of 2-(trimethylsilylmethyl)-3-ace-toxy-l-propene to electron-deficient double bonds bearing chiral auxiliaries is usually poorly stereoselective. However, face selectivity is interesting when using ephedrine-derived system 1.93 [352]. 

Preparative Methods. As discussed above, one of the simplest methods of preparation of 3-acetoxy-2-trimethylsilyhnethyl-1-propene (1) is the direct silylation of the C,0-dianion derived from methallyl alcohol, followed by 0-desilylation and subsequent acetylation (eq 1 However, because of laboratory safety concerns (use of large quantities of 10 M n-BuLi) one might choose another more user-friendly route such as the copper-mediated conversion of 2-chloromethylallyl chloride to 2-chloro-methylallyl trichlorosilane (5), followed by methylation and nucleophilic displacement of the chloride by an acetate (eq 18). Moreover, the intermediate 3-chloro-2-trimethylsilylmethyl-l-propene (6) is also a useful reagent in organic synthesis and in many aspects has similar reactivity to 1. Alternatives to 1 include the carbonate derivatives 7. 

Related Reagents. 3-Acetoxy-2-trimethylsilylmethyl-l-propene 1 3-Iodo-2-trimethylsilylmethyl-l-propene. 

---