Copper-Catalyzed Intermolecular Trifluoromethylthiocyanation of Alkenes: Convenient Access to CF₃-Containing Alkyl Thiocyanates

Abstract

A highly selective and efficient approach for the direct trifluoromethylthiocyanation of alkenes has been developed using trimethylsilyl isothiocyanate (TMSNCS) as the thiocyanating agent and Togni reagent as the CF3 source in the presence of copper(I) catalyst. Both activated and unactivated alkenes work well to deliver various CF3-containing thiocyanates.

A thiocyanopalladation/carbocyclization transformation identified through enzymatic screening: stereocontrolled tandem C–SCN and C–C bond formation

“…In particular, there are few such reaction manifolds for installing valuable C–SCN bonds. 2 , 3 Two issues loom large here, the longstanding documentation of TM-catalyst poisoning by thiol species 1a , 4 especially thiocyanate anion, 5 and the lability of the SCN functionality. 6 The title transformation emerged from a wider search for transformations of synthetic utility employing our in situ enzymatic screening (ISES) approach to reaction discovery.…”

Dual Photoredox/Copper Catalysis for the Remote C(sp3)−H Functionalization of Alcohols and Alkyl Halides by N‐Alkoxypyridinium Salts

“…Although thiocyanation of (hetero)arenes and alkenes have been well developed, [28] the thiocyanation of unactivated alkanes was,t ot he best of our knowledge, unknown. [29] Inspired by the recent work of Liu on the Cu-catalyzed enantioselective benzylic cyanation, we examined the catalytic enantioselective cyanation of 4a. [27] As the reaction liberates one equivalent of pyridine which is an excellent ligand for copper,t he difficulty associated with the development of catalytic enantioselective process is obvious.T o minimize the interference of the pyridine,tridentate (pybox) and bidentate (bisoxazoline) ligands were selected for this purpose (See the Supporting Information for ligand screen-ing).…”

Dual Photoredox/Copper Catalysis for the Remote C(sp3)−H Functionalization of Alcohols and Alkyl Halides by N‐Alkoxypyridinium Salts

“…Three representative examples involving the functionalization of benzylic, aliphatic, and tertiary C(sp 3 )−H are shown in Scheme . Although thiocyanation of (hetero)arenes and alkenes have been well developed, the thiocyanation of unactivated alkanes was, to the best of our knowledge, unknown …”