Asymmetric Stepwise Reductive Amination of Sulfonamides, Sulfamates, and a Phosphinamide by Nickel Catalysis

Abstract

Asymmetric reductive amination of poorly nucleophilic sulfonamides was realized in the presence of nickel catalysts and titanium alkoxide. A wide range of ketones, including enolizable ketones and some biaryl ones, were converted into sulfonamides in excellent enantiomeric excess. The cyclization of sulfamates and intermolecular reductive amination of a diarylphosphinamide were also successful. Formic acid was used as a safe and economic surrogate of high‐pressure hydrogen gas.

Nickel-Catalyzed Asymmetric Hydrogenation of Cyclic Sulfamidate Imines: Efficient Synthesis of Chiral Cyclic Sulfamidates

“…Recently, the Fe-, Co-, and Ni-catalyzed asymmetric hydrogenation of prochiral unsaturated compounds has received great attention, which shows the great potential of first-row transition metals in catalytic asymmetric (transfer) hydrogenation (Morris, 2009, Morris, 2015, Chirik, 2015, Li et al., 2014, Li et al., 2015, Li et al., 2017, Bauer and Knölker, 2015, Sui-Seng et al., 2008, Zhou et al., 2011, Monfette et al., 2012, Friedfeld et al., 2013, Friedfeld et al., 2016, Lagaditis et al., 2014, Sonnenberg et al., 2014, Lu et al., 2015, Chen et al., 2016, Hamada et al., 2008, Hibino et al., 2009, Dong et al., 2012, Yang et al., 2014, Yang et al., 2016, Guo et al., 2015, Xu et al., 2015, Shevlin et al., 2016, Gao et al., 2017, Zhao et al., 2019). Among these catalytic methodologies, Ni-catalyzed asymmetric hydrogenation is still in early stage, and there are a few related studies at present (Li et al., 2015, Li et al., 2017, Hamada et al., 2008, Hibino et al., 2009, Dong et al., 2012, Yang et al., 2014, Yang et al., 2016, Guo et al., 2015, Xu et al., 2015, Shevlin et al., 2016, Gao et al., 2017, Zhao et al., 2019). In 2008 and 2009, Hamada and co-workers reported Ni-catalyzed asymmetric hydrogenation of α-amino-β-ketoester hydrochlorides and substituted aromatic α-aminoketone hydrochlorides through dynamic kinetic resolution (Hamada et al., 2008, Hibino et al., 2009).…”

Primary Sulfonamide Synthesis Using the Sulfinylamine Reagent N-Sulfinyl-O-(tert-butyl)hydroxylamine, t-BuONSO

“…These include Knowles’ proton-coupled electron transfer process to generate sulfonamidyl radicals under mild photoredox conditions, which can then add in an anti-Markovnikov fashion to alkenes, 17 Stradiotto’s nickel-catalyzed cross-coupling of sulfonamides with (hetero)aryl chlorides, 18 and MacMillan’s Ir/Ni photocatalytic coupling of sulfonamides with (hetero)aryl halides. 19 A two-step nickel-catalyzed enantioselective reductive sulfonamidation of ketones 20 and the first reported application of sulfonamides in the Petasis reaction 21 were also recently disclosed.…”