A theory-driven synthesis of symmetric and unsymmetric 1,2-bis(diphenylphosphino)ethane analogues via radical difunctionalization of ethylene

Hideaki Takano, Hitomi Katsuyama, Hiroki Hayashi, Wataru Kanna, Yu Harabuchi, Satoshi Maeda () and Tsuyoshi Mita ()
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Hideaki Takano: Hokkaido University
Hitomi Katsuyama: Hokkaido University
Hiroki Hayashi: Hokkaido University
Wataru Kanna: Hokkaido University
Yu Harabuchi: Hokkaido University
Satoshi Maeda: Hokkaido University
Tsuyoshi Mita: Hokkaido University

Nature Communications, 2022, vol. 13, issue 1, 1-13

Abstract: Abstract 1,2-Bis(diphenylphosphino)ethane (DPPE) and its synthetic analogues are important structural motifs in organic synthesis, particularly as diphosphine ligands with a C2-alkyl-linker chain. Since DPPE is known to bind to many metal centers in a bidentate fashion to stabilize the corresponding metal complex via the chelation effect originating from its entropic advantage over monodentate ligands, it is often used in transition-metal-catalyzed transformations. Symmetric DPPE derivatives (Ar12P−CH2−CH2−PAr12) are well-known and readily prepared, but electronically and sterically unsymmetric DPPE (Ar12P−CH2−CH2−PAr22; Ar1≠Ar2) ligands have been less explored, mostly due to the difficulties associated with their preparation. Here we report a synthetic method for both symmetric and unsymmetric DPPEs via radical difunctionalization of ethylene, a fundamental C2 unit, with two phosphine-centered radicals, which is guided by the computational analysis with the artificial force induced reaction (AFIR) method, a quantum chemical calculation-based automated reaction path search tool. The obtained unsymmetric DPPE ligands can coordinate to several transition-metal salts to form the corresponding complexes, one of which exhibits distinctly different characteristics than the corresponding symmetric DPPE–metal complex.

Date: 2022
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DOI: 10.1038/s41467-022-34546-5

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