Mechanistic insights into the opening of epoxides with trimethylsilyl cyanide - zinc iodide

✍ Scribed by Paul G Gassman; Kentaro Okuma; Aline Lindbeck; Richard Allen

• Publisher: Elsevier Science
• Year: 1986
• Tongue: French
• Weight: 254 KB
• Volume: 27
• Category: Article
• ISSN: 0040-4039
• DOI: 10.1016/s0040-4039(00)87794-1

✦ Synopsis

endo-2,3-Epoxy-1,7,7-trimethylbicyclo[2.2.1]heptane reacted with trimethylsilyl cyanide in the pre=e of zinc iodide to produce a complex mixture of products. The major product, anti-7-trimethylsiloxy-endo-2,3,3-trimethyl-exo-2-isocyanobicyclo[2.2.l]heptane was obtained in f2%yield.

-In addition, eight other products were identified in yields ranging from 10% to 1%. All of the products could be rationalized on the basis of initial generation of a carbocationic intermediate.

Recently, we have described the opening of oxiranes (epoxides)3 and oxetanes4 with trimethylsilyl cyanide -zinc iodide to produce high yields of 1 and 2, respectively. Because of the ease with which lcould be converted into B-amino alcohols and 2 into y-amino alcohols,