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

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Title: A theory-driven synthesis of symmetric and unsymmetric 1,2-bis(diphenylphosphino)ethane analogues via radical difunctionalization of ethylene
Authors: Takano, Hideaki Browse this author
Katsuyama, Hitomi Browse this author
Hayashi, Hiroki Browse this author
Kanna, Wataru Browse this author
Harabuchi, Yu Browse this author
Maeda, Satoshi Browse this author
Mita, Tsuyoshi Browse this author →KAKEN DB
Issue Date: 21-Nov-2022
Publisher: Nature Portfolio
Journal Title: Nature communications
Volume: 13
Issue: 1
Start Page: 7034
Publisher DOI: 10.1038/s41467-022-34546-5
Abstract: 1,2-Bis(diphenylphosphino)ethane (DPPE) and its synthetic analogues are important structural motifs in organic synthesis, particularly as diphosphine ligands with a C-2-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 ((Ar2P)-P-1-CH2-CH2-PAr21) are well-known and readily prepared, but electronically and sterically unsymmetric DPPE ((Ar2P)-P-1-CH2-CH2-PAr22; Ar-1 not equal Ar-2) 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 C-2 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. DPPEs are fundamental bidentate ligands with a C2-alkyl-linker chain for many transition-metal-catalyzed reactions. Here, authors utilize the AFIR method to develop a practical synthetic method for both symmetric and unsymmetric DPPEs with ethylene.
Type: article
URI: http://hdl.handle.net/2115/87835
Appears in Collections:化学反応創成研究拠点:ICReDD (Institute for Chemical Reaction Design and Discovery : ICReDD) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

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