Rhodium(III)-Catalyzed Atroposelective Indolization to Access Planar-Chiral Macrocycles

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(42), P. 29214 - 29223

Published: Oct. 9, 2024

Macrocycles incorporating conformationally defined indoles are widely found in bioactive natural products. However, the catalytic enantioselective synthesis of planar-chiral via indolization involving macrocyclization remains elusive. Herein, we present first rhodium(III)-catalyzed atroposelective macrocyclization, which involves C-H activation aniline, and a subsequent oxidation [3 + 2] annulation reaction with an intramolecular alkyne. This protocol achieves construction indoles, planar chirality control single step. Importantly, this strategy produces macrocyclic atropisomers bearing full-carbon ansa chains, represent challenging targets organic synthesis. Thermodynamic experiments revealed that rotational barrier chain-linked atropisomer was lower than oxa-ansa chain. The mechanism elucidated by computational studies, alkyne insertion steps collectively determined enantioselectivity.

Language: Английский

---

Atropo‐Enantioselective Oxidation‐Enabled Iridium(III)‐Catalyzed C−H Arylations with Aryl Boronic Esters

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(34), P. 18532 - 18536

Published: June 21, 2021

Atropo-enantioselective biaryl coupling through C-H bond functionalization is an emerging technology allowing direct construction of axially chiral molecules. This approach largely limited to electrophilic partners. We report a highly atropo-enantioselective arylation tetralone derivatives paired with aryl boronic esters as nucleophilic components. The transformation catalyzed by cyclopentadienyl (Cpx ) iridium(III) complexes and enabled oxidatively enhanced reductive elimination from high-valent cyclometalated Ir-species.

Language: Английский

---

Chiral Allylic Amine Synthesis Enabled by the Enantioselective Cp^XRh(III)-Catalyzed Carboaminations of 1,3-Dienes

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(4), P. 2279 - 2287

Published: Feb. 5, 2021

Considering the importance of chiral allylic amine structural motif and rarity synthetic methods toward their construction, herein, we report a CpXRh(III)-catalyzed enantioselective intermolecular carboamination 1,3-dienes via N-phenoxy amides-derived aryl C–H activation intramolecular amide transfer. The methodology enables direct synthesis variety amines with embedment phenol functionalities proceeds under mild conditions sequential formation completely regioselective C–C bond highly C–N bond. Integrated experimental computational mechanistic studies reveal an unusual Rh(III)–Rh(I)–Rh(III) catalytic pathway, in which alkene insertion/π-allylation/intramolecular nucleophilic substitution cascade was involved for this transformation. Besides, application derivation natural products late-stage assembly bioactive complexes has also been demonstrated, further strengthens utility approach.

Language: Английский

---

Construction of C−C Axial Chirality via Asymmetric Carbene Insertion into Arene C−H Bonds

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(49), P. 25714 - 25718

Published: Oct. 1, 2021

By using diazonaphthoquinones and anilines as key reagents through a point-to-axis chiral transfer strategy, the atroposelective synthesis via asymmetric C(sp2 )-H bond insertion reaction of arenes has been realized under rhodium catalysis, providing resulting biaryl atropisomers in moderate to excellent yields with good enantiomeric ratios (up 99:1). Further elaboration indicates this type axially scaffold may have promising potentials developing novel ligands.

Language: Английский

---

Synthesis of N-Arylindoles from 2-Alkenylanilines and Diazonaphthalen-2(1H)-ones through Simultaneous Indole Construction and Aryl Introduction

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(11), P. 7392 - 7404

Published: May 20, 2022

In this paper, an efficient synthesis of N-arylindoles through the cascade reaction 2-alkenylanilines with diazonaphthalen-2(1H)-ones is presented. Mechanistically, involves generation a Ru-carbene complex from diazonaphthalen-2(1H)-one, followed by carbene N-H bond insertion 2-alkenylaniline, intramolecular cyclization, and oxidative aromatization. reaction, Ru(II) acts as multifunctional catalyst to promote not only formation but also cyclization dehydrogenative Meanwhile, air green cost-effective oxidant. To our knowledge, first example in which were synthesized simultaneous introduction N-aryl unit construction indole scaffold. Notable advantages method include readily accessible halide-free substrates, additive-free conditions, good efficiency, excellent atom economy, compatibility diverse functional groups. addition, utility product thus obtained was showcased its structural transformations.

Language: Английский

---