Site-Specific Deaminative Trifluoromethylation of Aliphatic Primary Amines.

The introduction of trifluoromethyl groups into organic molecules is of paramount importance in modern synthetic chemistry and medicinal chemistry. While methods for constructing C(sp )-CF bonds have been well established, the advancement of practical and comprehensive approaches for forming C(sp )-CF bonds remains considerably restricted. In this work, we describe an efficient and site-specific deaminative trifluoromethylation reaction of aliphatic primary amines to afford the corresponding alkyl trifluoromethyl compounds.

β-Boron Effect Enables Regioselective and Stereospecific Electrophilic Addition to Alkenes.

Electrophilic addition to alkenes is a textbook-taught reaction, yet it is not always possible to control the regioselectivity of addition to unsymmetrical 1,2-disubstituted substrates. We report the observation and applications of the β-boron effect that accounts for high regioselectivity in electrophilic addition reactions to allylic MIDA (-methyliminodiacetic acid) boronates. While the well-established β-silicon effect bears partial resemblance to the observed reactivity, the silyl group is typically lost during functionalization.

Deaminative bromination, chlorination, and iodination of primary amines.

The primary amino group has been seldom utilized as a transformable functionality in organic synthesis. Reported herein is a deaminative halogenation of primary amines using -anomeric amide as the nitrogen-deletion reagent. Both aliphatic and aromatic amines are competent substrates for direct halogenations.