scispace - formally typeset
Journal ArticleDOI

Catalytic and Enantioselective Control of the C–N Stereogenic Axis via the Pictet–Spengler Reaction

TLDR
In this article, an unprecedented example of a chiral phosphoric acid-catalyzed atroposelective Pictet-Spengler reaction of N-arylindoles is reported.
Abstract
An unprecedented example of a chiral phosphoric acid-catalyzed atroposelective Pictet-Spengler reaction of N-arylindoles is reported. Highly enantioenriched N-aryl-tetrahydro-β-carbolines with C-N bond axial chirality are obtained via dynamic kinetic resolution. The hydrogen bond donor introduced on the bottom aromatic ring, forming a secondary interaction with the phosphoryl oxygen, is essential to achieving high enantioselectivity. A wide variety of substituents are tolerable with this transformation to provide up to 98 % ee. The application of electron-withdrawing group-substituted benzaldehydes enables the control of both axial and point stereogenicity. Biological evaluation of this new and unique scaffold shows promising antiproliferative activity and emphasizes the significance of atroposelective synthesis.

read more

Citations
More filters
Journal ArticleDOI

Atropisomers beyond the C–C axial chirality: Advances in catalytic asymmetric synthesis

TL;DR: In this paper , a range of catalytic atroposelective approaches have been reported for the efficient synthesis of X-Y axially chiral skeletons. But, the intrinsic shorter bond length and electron-repelling effect lead to a congested hetero X−Y axis.
Journal ArticleDOI

Rational design and atroposelective synthesis of N–N axially chiral compounds

TL;DR: The first catalytic asymmetric synthesis of N–N axially chiral compounds has been accomplished via a quinidine catalyzed N-allylic alkylation reaction via DFT calculations to understand the origin of enantioselectivity and provide guidance for the design of additional molecules of this type.
Journal ArticleDOI

Asymmetric Synthesis of Axially Chiral C−N Atropisomers

TL;DR: A review of axially chiral C−N atropisomers can be found in this paper , where a brief introduction is given to contextualize these axially Chiral skeletons, including a historical background and examples of natural products containing axially CHN axes.
Journal ArticleDOI

Catalytic Asymmetric Synthesis of Axially Chiral 3,3'‐Bisindoles by Direct Coupling of Indole Rings

TL;DR: In this article , a new enantioselective synthesis strategy for axially chiral 3,3'-bisindoles was devised by the direct coupling of two indole rings.
Journal ArticleDOI

Synthesis of Axially Chiral N-Arylindoles via Atroposelective Cyclization of Ynamides Catalyzed by Chiral Brønsted Acids.

TL;DR: A facile access to axially chiral N-heterocycles enabled by chiral Brønsted acid-catalyzed 5-endo-dig cyclization of ynamides is disclosed, which represents the first metal-free protocol for the construction of axiallychiral compounds from ynamide.
References
More filters
Journal ArticleDOI

Chiral Brønsted acid-catalyzed direct Mannich reactions via electrophilic activation.

TL;DR: It was found that the phosphoric acid derivatives of general structure 1 serve as highly effective catalysts for the direct addition of acetyl acetone to N-Boc-protected arylimines and functions as an excellent catalyst.
Journal ArticleDOI

Atroposelective total synthesis of axially chiral biaryl natural products.

TL;DR: Gerhard Bringmann's research interests focus on the field of analytical, synthetic, and computational natural product chemistry, i.e., on axially chiral biaryls, which is characterized by a broad structural diversity.
Related Papers (5)