A5019564210- Cyclopropane Reaction Mechanisms
- Catalytic C–H Functionalization Methods
- X-ray Diffraction in Crystallography
- Asymmetric Synthesis and Catalysis
- Crystallization and Solubility Studies
- Asymmetric Hydrogenation and Catalysis
- Synthesis and Catalytic Reactions
- Molecular spectroscopy and chirality
- Axial and Atropisomeric Chirality Synthesis
- N-Heterocyclic Carbenes in Organic and Inorganic Chemistry
- Enzyme Catalysis and Immobilization
- Catalytic Cross-Coupling Reactions
- Crystallography and molecular interactions
- Synthesis of heterocyclic compounds
- Organic Chemistry Cycloaddition Reactions
Indian Institute of Science Bangalore
2022-2025
Traditional radical-mediated ring-opening of bicyclo[1.1.0]butanes (BCBs) for cyclobutane synthesis suffers from poor diastereoselectivity. Although few reports on BCB via polar mechanisms are available, the Lewis acid-catalyzed diastereoselective BCBs using carbon nucleophiles is still underdeveloped. Herein, we report a mild and Bi(OTf)3-catalyzed employing 2-naphthols. The anticipated carbofunctionalized trisubstituted cyclobutanes were obtained bicoordinated bismuth complex products...
Bicyclo[1.1.0]butanes (BCBs), featuring two fused cyclopropane rings, have found widespread application in organic synthesis. Their versatile reactivity towards radicals, nucleophiles, cations, and carbenes makes them suitable for various reactions, including ring-opening annulation strategies. Despite this versatility, their potential as enophiles an ene reaction remains underexplored. Considering given the challenges of achieving diastereoselectivity reactions BCBs, herein, we present a...
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...
Despite tremendous progress of dienamine catalysis along with its application in enantioselective synthesis over nearly two decades, certain limitations, especially respect to the regioselectivity generation step, continue persist. To overcome these shortcomings classical catalysis, we now introduce concept alkoxy-directed and apply it de novo arene construction by desymmetrizing meso-enediones through [4 + 2]-cycloaddition. Catalyzed a diphenylprolinol silyl ether, this reaction utilizes...
Abstract Transition-metal-catalysed asymmetric carbene insertion reactions into various X–H bonds typically suffer from poor stereoselectivity. It has been proposed that the presence of metal-free intermediates leads to erosion selectivity. In current account, we discuss our recent efforts understand mechanism and stereochemical model Rh- Fe-catalysed indole phenol. Our detailed DFT calculations show all transformations adopt a common involving an enol intermediate, further tautomerisation...
The mechanism of Rh2 (S-NTTL)4 catalyzed carbene insertion into C(3)-H indole is investigated using DFT methods. Since the commonly accepted enol cannot account for enantioinduction, a concerted oxocarbenium pathway was proposed in an earlier work model catalyst. However, after considering full catalytic system, this study finds that akin to other reactions, here, too, lower energy, which now naturally raises conundrum regarding mode chiral induction. Herein, new water promoted mechanistic...
Central chirality in arene derivatives arising out of unsymmetrically substituted ring is a fascinating yet rarely explored research topic. Here, we report desymmetrization approach to centrally chiral unfunctionalized arenes, which enabled by the enantioselective de novo construction ring. This operationally simple protocol based on [4+2]-cycloaddition between polycyclic meso-cyclohexenediones and α,β-unsaturated aldehydes, doesn't usually require any external oxidant. Catalyzed...
Abstract Central chirality in arene derivatives arising out of unsymmetrically substituted ring is a fascinating yet rarely explored research topic. Here, we report desymmetrization approach to centrally chiral unfunctionalized arenes, which enabled by the enantioselective de novo construction ring. This operationally simple protocol based on [4+2]‐cycloaddition between polycyclic meso ‐cyclohexenediones and α,β‐unsaturated aldehydes, doesn't usually require any external oxidant. Catalyzed...