Visible-light-promoted aerobic metal-free aminothiocyanation of activated ketones

Abstract

A direct, redox-neutral, highly atom-economical and metal-free aerobic method for the synthesis of multi-substituted olefins via simply coupling ammonium thiocyanate with activated ketones is described.

Sustainable Synthetic Approaches Involving Thiocyanation and Sulfur- Cyanation: An Update

“…By coupling ammonium thiocyanate with activated ketones (56) under photocatalysis conditions, using air as the terminal oxidant, (E)-3-amino-2-thiocyanato-α,β-unsaturated compounds (57) were obtained in large variety, in good to excellent yields (Scheme 23) [23]. The ammonium thiocyanate was doubly used as an amine and thiocyanate source, and water was the only byproduct.…”

in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling with Enaminone Derivatives Under Transition‐metal Free Conditions

“…[1] On the other hand, there has been long-standing interest in the construction of CÀ S/Se bonds because of their important applications in organic synthesis [2] and the broad biological properties associated with S or Se-containing compounds. [4] Furthermore, α-thioenamine compounds are also potential scaffolds found in pharmaceutical and bioactive molecules. This might also be attributed to the fact that they could be conveniently converted into multifunctional compounds through asymmetric hydrogenation.…”

“…[4,6] Among these strategies, one of the most straightforward methods is by the means of direct C(sp 2 )-S bond formation through CÀ H bond functionalization of the alkene moiety in the enamine substrates. [4,6] Among these strategies, one of the most straightforward methods is by the means of direct C(sp 2 )-S bond formation through CÀ H bond functionalization of the alkene moiety in the enamine substrates.…”

“…This might also be attributed to the fact that they could be conveniently converted into multifunctional compounds through asymmetric hydrogenation. [4] Furthermore, α-thioenamine compounds are also potential scaffolds found in pharmaceutical and bioactive molecules. [5] For example, compound I, [5a,b] which is known as an inhibitor for Cdc25B dual specificity protein phosphatase, possesses a thioenamine scaffold in its structure.…”

“…Hence, tremendous effort has been devoted to the construction of the α-thioenamine skeleton, which combines structural diversity with interesting biological activities. [4,6] Among these strategies, one of the most straightforward methods is by the means of direct C(sp 2 )-S bond formation through CÀ H bond functionalization of the alkene moiety in the enamine substrates. The transition metal-free CÀ H bond func-tionalization of enamines has recently witnessed notable advances.…”