Improved Cope-type hydroamination reactivity of hydrazine derivatives

Abstract

A systematic investigation on the metal-free, Cope-type hydroamination reactivity of hydrazides and analogues is reported. Optimization of the hydrazide structure resulted in more facile intramolecular reactivity and enabled intermolecular reactions of alkenes, thus providing a direct approach to polysubstituted hydrazides.

Cascade reactions of nitrogen-substituted isocyanates: a new tool in heterocyclic chemistry

“…amines) on N -isocyanates would be essentially irreversible. Building on our expertise in metal-free hydroamination reactions of hydrazine derivatives, 10 we developed an N -isocyanate addition/Cope-type hydroamination cascade for the formation of saturated nitrogen heterocycles (eqn (2)), illustrated below using blocked N -isocyanate 1a . 7 …”

Aqueous hydrazine as a promising candidate for capturing carbon dioxide

“…Niemeier and Kjell (2013) reported that dilution plays an important role in increasing the intrinsic safety of aqueous hydrazine. Aqueous hydrazine, instead of hydrazine, is thus used as a blowing agent (Berins, 2002) and a precursor to make various high-value chemicals widely (Loiseau et al, 2011;Silva et al, 2008).…”

Formal anti-Markovnikov hydroamination of terminal olefins

“…18 However, these metal-catalyzed hydroamination methodologies have various limitations such as harsh basic conditions, the requirement of a directing group, and limited substrate scopes. Two additional approaches from the Studer 19 and Beauchemin 20 groups accomplish this transformation through free radical and pericyclic additions, respectively, although selectivity is substrate-dependent in the latter case. 21 Despite considerable advances in the area of metal-catalyzed anti-Markovnikov hydroaminations of olefins, a general method remains an elusive goal.…”