A Facile Synthesis of a Key Intermediate for (+)-Biotin via Strecker Reaction

Abstract

The Strecker reaction of (2R,4R)-2-phenyl-3-phenoxycarbonylthiazolidine-4-carbaldehyde (4b), which was readily prepared from l-cysteine, with benzylamine and trimethylsilyl cyanide provided α-amino nitrile 5b stereoselectively (syn-anti, 2:1). Amidation of 5b and subsequent cyclization gave bicyclic compound 6, which, upon reduction with zinc dust, hydrolysis and subsequent cyclization, furnished thiolactone 2, a key intermediate for (+)-biotin (1).

Keywords

amino acids - amino aldehydes - ring closure - stereo­selectivity - vitamins - biotin - Strecker reaction

References

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8

The X-ray data of syn-5a have been deposited at the Cambridge Crystallographic Data Centre.

13

Poetsch and Casutt of the Merck Laboratories synthesized the bicyclic intermediate 14 through reduction of a carbonyl group of bicyclic hydantoin 13 derived from l-cysteine followed by formation of the corresponding imidazolide, cyanation and hydrolysis (Scheme [6] ). [5]
Although the approach can provide 2 in 9 steps, it requires expensive or hazardous reagents such as BnNCO and CDI.