[74379-74-1] · C12H18SSi · 1-(Phenylthio)-1-(trimethylsilyl)cyclopropane · (MW 222.46)
Physical Data: bp 64 °C/0.1 mmHg; d 0.991 g cm-3.
Form Supplied in: liquid; commercially available.
Purification: by distillation.1b
Handling, Storage, and Precautions: use in a fume hood.
1-Lithio-1-(trimethylsilyl)cyclopropane, derived from 1-phenylthio-1-(trimethylsilyl)cyclopropane by reductive lithiation with Lithium 1-(Dimethylamino)naphthalenide (LDMAN), condenses with aldehydes to give carbinols which are converted to alkylidenecyclopropanes under Peterson alkenation conditions (eq 1).1
m-Chloroperbenzoic Acid oxidation of 1-phenylthio-1-(trimethylsilyl)cyclopropane furnishes a sulfoxide which could undergo thermal sila-Pummerer rearrangement to give the masked cyclopropanone 1-(phenylthio)-1-trimethylsiloxy)cyclopropane (eq 2).2a
Alternative treatment of the sulfoxide with aldehydes in the presence of Tetra-n-butylammonium Fluoride gives the phenylsulfinylcarbinol and thence the phenylthiocarbinol following reduction. The two last-named compounds are intermediates in the synthesis of cyclobutanones and cyclobutenes, respectively (eqs 3 and 4).2b,2c,2e
Condensation of 1-lithio-1-(trimethylsilyl)cyclopropane with ketones gives vinylcyclopropane intermediates, which upon pyrolysis undergo vinylcyclopropane rearrangement to give annulated cyclopentene derivatives (eq 5).3
Uko E. Udodong
Eli Lilly and Company, Indianapolis, IN, USA