Synthetic applications of trimethylsilyl cyanide. Efficient synthesis of .beta.-aminomethyl alcohols

Abstract

The use of trimethylsilyl cyanide (TMSCN) as a reagent for the direct formation of trimethylsilyl cyanohydrin ethers 3 from ketones is reported. The advantages in using TMSCN as opposed to hydrogen cyanide are illustrated by the formation of cyanohydrin ethers of ketones that do not form stable cyanohydrins. The reduction of derivatives 3 with lithium aluminum hydride is reported to afford /3-aminomethyl alcohols 4 in good yield. The combined carbonyl derivatization-reduction sequence should afford a general synthesis of 4 useful in executing ring expansion reactions.

New synthesis of mephenoxalone

“…The silyl ether 11 was reduced using LiAlH 4 giving the β-aminoalcohol 12 with 63 % yield. 26 The final step consisted in the cyclization of 12 with BTC to give the oxazolidinone 1 in 70% yield (Scheme 2). The overall yield from aldehyde 10 to Mephenoxalone (1) was 42%.…”

2,2′-Bis(4-methoxyphenyl)-2,2′-bis(trimethylsilanyloxy)-2,2′-(ferrocene-1,1′-diyl)diacetonitrile

“…Cyanohydrin trimethylsilyl ethers are useful in organic synthesis as they serve not only for the protection of carbonyl groups (Rasmussen et al, 1978;Groutas et al, 1980;Fischer et al, 1987) but also as versatile intermediates (Gassman et al, 1978;Evans et al, 1974;Fleming et al, 1979) in the synthesis of cyanohydrins, α,β-unsaturated nitriles and β-aminoalcohols. The general method for the preparation of cyanohydrin trimethylsilyl ethers is the addition of trimethylsilyl cyanide (TMSCN) to carbonyl compounds with the aid of a catalyst including Lewis acids, such as ZnI 2 (Evans et al,1974) and AlCl 3 (Lidy et al, 1973), as well as solubilized anionic species, such as K + CN --18-Crown-6 and n Bu 4 N + CN - (Evans et al,1973).…”

“…For related literature, see: Evans & Truesdale (1973); Evans et al (1974); Lidy & Sundermeyer (1973); Dunitz et al (1956); Fischer & Hü ning (1987) ;Fleming & Woolias (1979); Gassman & Talley (1978); Groutas & Felker (1980); Rasmussen & Heilmann (1978); Zhou (1989).…”

An unexpected acyloin rearrangement and oxidation of a camphor derivative

“…The mixture of cyanohydrin ether stereoisomers 6 was prepared in 95% yield as previously described (7). Reduction of 6 with 'Author to whom correspondence may be addressed.…”