A facile synthesis of biologically important S-aryl dithiocarbamates has been demonstrated by the aryne three-component coupling involving CS2 and aliphatic amines. This transition-metal-free and mild reaction is scalable and operates with good functional group compatibility. Preliminary mechanistic experiments, including density functional theory studies, are also provided. Moreover, with 3-triflyloxybenzynes, a unique four-component coupling incorporating tetrahydrofuran was observed.

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C−C bonds is wellknown, the synthesis of axially chiral C−N bond-containing compounds is relatively less explored, and the construction of axially chiral N−N bonds has received only scant attention. Demonstrated herein is the N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction, leading to the atroposelective synthesis of N−N axially chiral 3-amino quinazolinones. The NHC-catalyzed reaction of quinazolinones containing a free N−H moiety with α,β-unsaturated aldehydes under oxidative conditions furnished the atropisomeric quinazolinone derivatives under mild conditions and broad scope. Preliminary studies on experimental and density functional theory-based N−N rotational barrier determination are also presented.

Although the atroposelective synthesis of biaryls and related compounds bearing axially chiral C-C bonds are well-known, the synthesis of axially chiral C-N bond-containing compounds are relatively less explored, and the construction of axially chiral N-N bonds has received only scant attention. Demonstrated herein is the N-heterocyclic carbene (NHC)-catalyzed selective amidation reaction leading to the atroposelective synthesis of N-N axially chiral 3-amino quinazolinones. The NHC-catalyzed reaction of quinazolinones containing a free N-H moiety with -unsaturated aldehydes under oxidative conditions furnished the atropisomeric quinazolinone derivatives under mild conditions and broad scope. Preliminary studies on experimental and DFT-based N-N rotational barrier determination is also presented.

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We computationally study the mechanistic pathway for the synthetically valuable cascading N–H functionalization followed by the C–C bond-forming reaction. The impetus to study such multicomponent reactions catalyzed by Rh­(I) arises from the highly fluxional nature of the onium ylide involved, which is often not amenable to experimental detection. Our results throw light on an interesting mechanistic paradigm where the binding of the ylide to the metal plays a crucial role. The study provides some much-needed insights to expand the scope of these highly valuable methodologies to a broader range of asymmetric reactions.