A method of SPINOL-derived chiral phosphoric acid catalyzed asymmetric intermolecular N-hydroxyalkylation of multisubstituted indoles with ethyl glyoxalates is described in this report. This protocol provides an alternative, convenient, and direct strategy for efficient access to structurally unique α-chiral indole N,O-acyclic aminals with a broad substrate scope and good to excellent enantioselectivities. The synthetic utility of this methodology is illustrated by a gram-scale experiment and the subsequent efficient synthesis of more complex chiral N,O-aminal indole derivatives.
The first examples
of electrochemical trifluoromethylation and
sulfonylation/semipinacol rearrangements of allylic alcohols were
developed using cheap and stable RSO2Na (R = CF3, Ph) as reagents. Various β-trifluoromethyl and sulfonated
ketones were obtained in moderate to excellent yields. This strategy
provides a facile, direct, and complementary approach to construct
all-carbon quaternary stereocenters. In addition, the reaction has
the advantages of being chemical oxidant-free and metal-free and has
safe and mild reaction conditions.
An efficient and convenient ligand-free, rhodium-catalyzed ortho-C(sp2)-H amidation of benzaldehydes with dioxazolones using H2O as the key promoter is described. Using this protocol, a wide range of benzaldehyde substrates were selectively amidated in good to excellent yields with broad functional group compatibility. KIE experiments revealed that the C-H bond activation was likely the rate-limiting step. In addition, computational studies indicated that the catalyst precursor interacted with water and dioxazolones to generate the active catalytic species. Notably, the practicality and efficacy of this method were illustrated by a late-stage amidation of an estrone-derived molecule and further transformations of the amidated product.
An efficient and environmentally benign Cu-mediated method was developed for direct cascade C-H/N-H annulation to construct polyheterocyclic indoloquinoline scaffolds. This method highlights an emerging strategy for transforming inert C-H bonds into versatile functional groups in organic synthesis and provides a new versatile approach for the efficient synthesis of indolo[3,2-c] and [2,3-c]quinoline alkaloids.
Nonbiaryl N-C atropisomer is an important structural scaffold, which is present in natural products, medicines and chiral ligands. However the direct enantioselective C-H amination to access optically pure N-C atropisomer is still difficult and rare. Here we report a π-π interaction and dual H-bond concerted control strategy to develop the chiral phosphoric acids (CPAs) catalyzed direct intermolecular enantioselective C-H amination of N-aryl-2-naphthylamines with azodicarboxylates as amino sources for the construction of atroposelective naphthalene-1,2-diamines. This type of N-C atropisomers is stabilized by intramolecular hydrogen bond and the method features a broad range of substrates, high yields and ee values, providing a strategy to chirality transfer via the modification of N-C atropisomers.
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