541508-57-0Relevant articles and documents
An efficient and practical procedure for Strecker reaction: A highly diastereoselective synthesis of a key intermediate for (+)-biotin
Seki, Masahiko,Hatsuda, Masanori,Yoshida, Shin-Ichi
, p. 6579 - 6581 (2004)
Treatment of α-amino aldehyde 2, which was prepared through Moffatt oxidation of the corresponding β-amino alcohol 5, with aqueous sodium bisulfite allowed clean conversion to a water-soluble bisulfite adduct 6 [>99% conversion, 89% yield (two steps)]. The aqueous solution of 6 was treated with benzylamine followed by easy-handling NaCN to effect the Strecker reaction to afford α-amino nitrile 3 with high diastereoselectivity and in high yield (syn/anti = 11:1, 95% assay yield). Both the compounds syn-3 and anti-3 were converted to a key intermediate 4 for (+)-biotin through S,N-carbonyl migration in high yields.
A practical synthesis of (+)-biotin from L-cysteine
Seki, Masahiko,Hatsuda, Masanori,Mori, Yoshikazu,Yoshida, Shin-Ichi,Yamada, Shin-Ichi,Shimizu, Toshiaki
, p. 6102 - 6110 (2007/10/03)
α-Amino aldehyde 4, which is readily derived from L-cysteine through cyclization and elaboration of the carboxy group, was subjected to the Strecker reaction, which, via sodium bisulfite adduct 16, afforded α-amino nitrile 5 with high diastereose-lectivity (syn/anti = 11:1) and in high yield. Amide 6, derived from 5, was converted to thiolactone 8, a key intermediate in the synthesis of (+)-biotin (1), by a novel S,N-carbonyl migration and cyclization reaction. The Fukuyama coupling reaction of 8 with the zinc reagent 21, which has an ester group, in the presence of a heterogeneous Pd/ C catalyst allowed the efficient installation of the 4-carboxybutyl chain to provide 9. Compound 9 was hydrogenated and the protecting groups removed to furnish 1 in 10 steps and in 34 % overall yield from L-cysteine.
2-Thiazolidinone: A novel thiol protective surrogate of complete atom efficiency, a practical synthesis of (+)-biotin
Seki, Masahiko,Kimura, Mayumi,Hatsuda, Masanori,Yoshida, Shin-Ichi,Shimizu, Toshiaki
, p. 8905 - 8907 (2007/10/03)
2-Thiazolidinone derivatives were shown to be novel protective surrogates of a thiol group in L-cysteine derivatives. After elaboration at the C-4 substituent, the thiol group was completely liberated by simple heating in DMF whose atom efficiency is 100%. A practical synthesis of (+)-biotin was accomplished by the use of the strategy employing 4-functionalized 2-thiazolidinone derivatives as the intermediates, allowing a synthesis of (+)-biotin in 10 steps and in 31% overall yield. Short steps, high yield, and ease of operation of the present approach would permit the hitherto most efficient access to (+)-biotin.
