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