Why Does Rh Prefer [4 + 1] while Pd Prefer [4 + 4 + 1] Mode in Carbocyclization of Vinylallene with CO? Unveiling Nickel’s Potential for Expanding the Scope Beyond Pd DOI

Sheetal Ranaut,

Shivnath Mazumder

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Rhodium(I) promotes a [4 + 1] assembly mode with vinylallene substrate and CO, leading to the formation of five-membered ring structure. In striking contrast, palladium(0) catalyzes more complex 4 nine-membered cyclic ketone. The underlying mechanisms that govern this contrast in modes remain unclear, even today's date, presenting major challenge further development efficient reactions. Our computational study reveals Rh adopts square pyramidal geometry CO. This is Pd, which prefers trigonal planar geometry. A stronger metal-CO interaction detected than Pd intermediate, making preferable Pd. transition state for C-C coupling between two has significantly distorted tetrahedral core case Rh, while retains stable structure, reaction less favorable By conceptualizing transferring critical features Ni systems, we have rationally designed Ni-catalyzed version combines desirable reactivity cost-effectiveness abundance Ni, aligning growing demand sustainable atom-efficient strategies synthetic organic chemistry.

Language: Английский

Why Does Rh Prefer [4 + 1] while Pd Prefer [4 + 4 + 1] Mode in Carbocyclization of Vinylallene with CO? Unveiling Nickel’s Potential for Expanding the Scope Beyond Pd DOI

Sheetal Ranaut,

Shivnath Mazumder

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 14, 2025

Rhodium(I) promotes a [4 + 1] assembly mode with vinylallene substrate and CO, leading to the formation of five-membered ring structure. In striking contrast, palladium(0) catalyzes more complex 4 nine-membered cyclic ketone. The underlying mechanisms that govern this contrast in modes remain unclear, even today's date, presenting major challenge further development efficient reactions. Our computational study reveals Rh adopts square pyramidal geometry CO. This is Pd, which prefers trigonal planar geometry. A stronger metal-CO interaction detected than Pd intermediate, making preferable Pd. transition state for C-C coupling between two has significantly distorted tetrahedral core case Rh, while retains stable structure, reaction less favorable By conceptualizing transferring critical features Ni systems, we have rationally designed Ni-catalyzed version combines desirable reactivity cost-effectiveness abundance Ni, aligning growing demand sustainable atom-efficient strategies synthetic organic chemistry.

Language: Английский

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