Rhodium(II)-Catalyzed Alkynyl Carbene Insertion into N–H Bonds DOI
Akashdeep Sharma,

Himani Vaid,

Riya Kotwal

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4887 - 4892

Published: June 6, 2024

The first insertion of an alkynyl carbene into N–H bonds under Rh-catalysis is developed. Alkynyl hydrazone carboxylates are used as donor–acceptor precursors and exquisitely inserted the various amines, amides, 1,2-diamines. A wide variety 3-alkynyl 3,4-dihydroquinoxalin-2(1H)-ones densely functionalized α-alkynyl α-amino esters obtained in good to excellent yields. Further, chemoselective reactions, mechanistic studies, synthetic transformations for obtaining valuable heterocycles demonstrated.

Language: Английский

Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles DOI

Kriti Gupta,

Mahesh Singh Harariya,

Arushi Tyagi

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(4)

Published: Jan. 11, 2024

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation side‐products. In this context, transition catalyzed onium ylides generated via diazo precursors nucleophiles with third component (an electrophile) have garnered significant attention. Using allylic precursor as electrophilic partner provides opportunities to construct all‐carbon centres. Furthermore, presence allyl fragment multicomponent product serves pivotal handle for carrying out subsequent modifications. Several recent studies employed Rh, Pd, dual Rh/Pd catalytic systems involving alkylation that proceed synergistic or relay pathway. Although not significantly successful, few cases, asymmetric induction achieved through chiral phosphoric acids phosphine ligands. Limited substrate catalyst scope underlying mechanistic complexities posed formidable challenges, slowing advancement reactions. This review details using readily available like compounds, carbonates, (R‐OH, R‐NH 2 , etc .) forming complex organic compounds. Our primary objective discuss issues may facilitate progress field.

Language: Английский

Citations

6
Mechanism and stereoselectivity in metal and enzyme catalyzed carbene insertion into X–H and C(sp2)–H bonds DOI
Reena Balhara, Ritwika Chatterjee, Garima Jindal

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(22), P. 11004 - 11044

Published: Jan. 1, 2024

This review provides a mechanistic overview of asymmetric Fe, Cu, Pd, Rh, Au and heme-based enzymes catalyzed carbene insertion reactions to construct C–X (X = O, N, S, etc. ) C–C bonds, focusing on the stereochemical models.

Language: Английский

Citations

4
Unveiling the Importance of Catalyst Framework and Non Covalent Interactions in an Asymmetric Fe-Catalyzed O–H Insertion: Insights from Computational Tools DOI
Reena Balhara, Garima Jindal

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(75), P. 10322 - 10325

Published: Jan. 1, 2024

Fe-based catalysts as well enzymes typically yield low stereoselectivity for carbene insertion into X-H bonds. Here, we have utilized DFT methods to understand the mechanism and unusually high enantioselectivity in an Fe-spiroBox catalyzed reaction O-H bond of aliphatic alcohols. Our transition state model shows a unique binding intermediates chiral catalyst enabled by weak non covalent interactions that is absent other reactions.

Language: Английский

Citations

2
Rhodium(II)-Catalyzed Alkynyl Carbene Insertion into N–H Bonds DOI
Akashdeep Sharma,

Himani Vaid,

Riya Kotwal

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4887 - 4892

Published: June 6, 2024

The first insertion of an alkynyl carbene into N–H bonds under Rh-catalysis is developed. Alkynyl hydrazone carboxylates are used as donor–acceptor precursors and exquisitely inserted the various amines, amides, 1,2-diamines. A wide variety 3-alkynyl 3,4-dihydroquinoxalin-2(1H)-ones densely functionalized α-alkynyl α-amino esters obtained in good to excellent yields. Further, chemoselective reactions, mechanistic studies, synthetic transformations for obtaining valuable heterocycles demonstrated.

Language: Английский

Citations

0