Synthesis of Optically Active α-Trifluoromethylamines by Rearrangement of β-Amino-α-trifluoromethyl Alcohols

Abstract

The synthesis of various optically active α-trifluoromethylamines has been realized from β-amino-α-trifluoromethyl alcohols via an aziridinium ion intermediate under kinetic conditions.

Diethylaminosulfur Trifluoride (DAST) Mediated Transformations Leading to Valuable Building Blocks and Bioactive Compounds

“…The opening of the resulting aziridinium ion 15 is favored on nontrifluoromethylated carbon. [22] In this case the rearranged products can also be obtained with very good yields. The synthesized β-amino-αtrifluoromethyl alcohols 16 can be used as valuable building Scheme 1.…”

“…The authors have presented usability of 16 in the syntheses of dipeptide analogues. [22] Fluorinated aminophosphonates and aminophosphonic acids belong to a group of interesting compounds from the perspective of broad medical applications. [23] Starting from αhydroxy-β-aminophosphonates 17, Kaźmierczak et al showed that depending on the fluorinating reagent used, regioselective control of the opening of resulting aziridinium ion 18 is possible (Scheme 5).…”

Synthetic Applications of Aziridinium Ions

“…A similar reaction with the fluoride nucleophile yielded a fluorinated product after the formation of an aziridinium ion driven by DAST [58]. The synthesis of various optically active α-trifluoromethyl amines (33) was realized from β-amino-α-trifluoromethylalcohols (31) via an aziridinium ion intermediate (32) under a kinetic condition (Scheme 10) [59].…”

Vicinal difunctionalization of carbon–carbon double bond for the platform synthesis of trifluoroalkyl amines

“…Other halides and pseudohalides were utilized in the second reaction step and the corresponding products (79-83) were isolated in 71-83% yield range. Interestingly, the 1,1,1,3-tetrafluoropropyl moiety previously had limited options in the literature for its preparation 50,72 . Therefore, N-allyl-PMB-amine and N-pyrid-2-ylpiperazine were utilized to demonstrate the feasibility of conditions II in the synthesis of various tetrafluoropropylamines (84, 85).…”

“…1e) [41][42][43][44] . In this respect, the syntheses of homo-and heterofunctionalized, α-trifluoromethyl vicinal diamines [45][46][47][48][49][50][51][52] and other substituted trifluoropropylamines [52][53][54][55] are demanding.…”