Burger K, Hennig L, Tsouker P, Spengler J, Albericio F, Koksch B
Department of Organic Chemistry, University of Leipzig, Leipzig, Germany.
Amino Acids. 2006 Jul;31(1):55-62. doi: 10.1007/s00726-006-0322-1. Epub 2006 May 22.
5-Benzyloxy-4-trifluoromethyl-1,3-oxazoles, obtained from 5-fluoro-4-trifluoromethyloxazoles and benzyl alcohols, are capable for rearrangements. A 1,3 shift of a benzyl group is the key step of a new general route toward alpha-trifluoromethyl substituted aromatic and heteroaromatic amino acids, demonstrating that 5-fluoro-4-trifluoromethyl-1,3-oxazole is a synthetic Tfm-Gly equivalent. On reaction with benzpinacol partially fluorinated oxazoles are transformed into bis(trifluoromethyl) substituted 2,5-diamino adipic acid and N-benzoyl-2-benzhydryl-3,3,3-trifluoroalanine.
由5-氟-4-三氟甲基恶唑与苄醇制得的5-苄氧基-4-三氟甲基-1,3-恶唑能够发生重排反应。苄基的1,3迁移是通往α-三氟甲基取代的芳香族和杂芳香族氨基酸新通用路线的关键步骤，这表明5-氟-4-三氟甲基-1,3-恶唑相当于合成的Tfm-Gly。与频哪醇二苯甲酮反应时，部分氟化的恶唑会转化为双（三氟甲基）取代的2,5-二氨基己二酸和N-苯甲酰基-2-二苯甲基-3,3,3-三氟丙氨酸。
