The Role of Xantphos in forming an Elusive dirhodium-η1-allyl Intermediate in a Rh(II)-Catalyzed Allylic Alkylation: A Combined Computational and Experimental Study DOI Creative Commons
Anubhav Goswami,

Romin Gogoi,

Arpita Panda

et al.

Published: May 30, 2023

The use of dirhodium tetracarboxylate catalysts in multicomponent reactions involving allylic alkylation has been a formidable challenge to synthetic chemists. A unique strategy by means catalyst structure modification the presence an external ligand, Xantphos, recently enabled their efficient one-pot carbene insertion into X–H bonds followed alkylation. However, origin novel reactivity and mechanism such remain unclear. Herein, we report combined computational experimental mechanistic study shed light on ligand-enabled its implication catalysis. This is dissociation octanoate bridge driven κ2-Xantphos ligation core catalyst. turn allows for hitherto unknown oxidative addition with Rh(II) resulting dirhodium-η1-allyl species. For first time, confirm species solution through situ NMR cyclic voltammetry experiments line DFT calculations. Alongside, role base solvent generating nucleophilic partner that can trap electrophilic expected guide future design, including chiral variants, exploring newer modes selectivity using

Language: Английский

The Role of Xantphos in forming an Elusive dirhodium-η1-allyl Intermediate in a Rh(II)-Catalyzed Allylic Alkylation: A Combined Computational and Experimental Study DOI Creative Commons
Anubhav Goswami,

Romin Gogoi,

Arpita Panda

et al.

Published: May 30, 2023

The use of dirhodium tetracarboxylate catalysts in multicomponent reactions involving allylic alkylation has been a formidable challenge to synthetic chemists. A unique strategy by means catalyst structure modification the presence an external ligand, Xantphos, recently enabled their efficient one-pot carbene insertion into X–H bonds followed alkylation. However, origin novel reactivity and mechanism such remain unclear. Herein, we report combined computational experimental mechanistic study shed light on ligand-enabled its implication catalysis. This is dissociation octanoate bridge driven κ2-Xantphos ligation core catalyst. turn allows for hitherto unknown oxidative addition with Rh(II) resulting dirhodium-η1-allyl species. For first time, confirm species solution through situ NMR cyclic voltammetry experiments line DFT calculations. Alongside, role base solvent generating nucleophilic partner that can trap electrophilic expected guide future design, including chiral variants, exploring newer modes selectivity using

Language: Английский

Citations

0