Mifleur, Alexis’s team published research in ACS Catalysis in 2017 | CAS: 210169-54-3

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.Reference of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

In 2017,Mifleur, Alexis; Merel, Delphine S.; Mortreux, Andre; Suisse, Isabelle; Capet, Frederic; Trivelli, Xavier; Sauthier, Mathieu; Macgregor, Stuart A. published 《Deciphering the Mechanism of the Nickel-Catalyzed Hydroalkoxylation Reaction: A Combined Experimental and Computational Study》.ACS Catalysis published the findings.Reference of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole The information in the text is summarized as follows:

The [Ni(COD)2]/P∩P-catalyzed hydroalkoxylation of butadiene to form butenyl ethers is studied mechanistically, where P∩P = 1,4-bis(diphenylphosphino)butane (dppb) and 1,2-bis(diphenylphosphinomethyl)benzene (dppmb). Exptl. studies suggest the intermediacy of [(P∩P)Ni(0)(butadiene)] and [(P∩P)Ni(II)(allyl)] intermediates and rule out the involvement of Ni-H species. The related species [(dppb)Ni(1,4-diphenylbutadiene)], 1, and [(P∩P)Ni(crotyl)(Cl)] complexes 2 (P∩P = dppmb) and 3 (P∩P = dppb) have been synthesized and characterized on the basis of VT NMR spectroscopy and X-ray crystallog. studies. 2 And 3 are shown to be catalytically competent for the hydroalkoxylation reaction. Computational studies on [(dppmb)Ni(butadiene)] indicate a facile protonation that form a cationic allylic intermediate [(dppmb)Ni(η-C4H7)]OMe. C-O bond formation then occurs via external attack by the solvent-stabilized methoxide nucleophile. Hydroalkoxylation proceeds with modest computed barriers of ca. 15 kcal/mol and the butenyl ether product formation is only marginally exergonic, consistent with a reversible process operating under thermodn. control. After reading the article, we found that the author used (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3Reference of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole)

(S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole(cas: 210169-54-3) is a chelating ligand used to prepare coordination complex catalysts, such as its use in Pd catalysts for the enantioselective synthesis of spiro- or benzofused hetereocycles with exocyclic olefins via enantioselective intramolecular dearomative Heck reaction of indoles, benzofurans, pyrroles and furans.Reference of (S)-5,5′-Bis(diphenylphosphino)-4,4′-bi-1,3-benzodioxole

Referemce:
Phosphine ligand,
Chiral phosphines in nucleophilic organocatalysis