158748-69-7Relevant articles and documents
Rhodium-Catalyzed Isomerization of a Bis(secondary phosphine) to an Unsymmetrical Diphosphine via P-C Cleavage and P-P and C-H Bond Formation
Scheetz, Perry M.,Glueck, David S.,Rheingold, Arnold L.
, p. 3387 - 3397 (2017)
To develop Rh-catalyzed dehydrocoupling for stereocontrolled synthesis of P-P bonds, we prepared potential intermediates, chiral rhodium phosphine-phosphido complexes, and investigated their stoichiometric and catalytic transformations. Treatment of [Rh(diphos)(COD)][X] with the bis(secondary phosphine) IsHPCH2PHIs (1, Is = 2,4,6-(i-Pr)3C6H2) gave the cations [Rh(diphos)(IsHPCH2PHIs)][X] (diphos? = (R,R)-Me-DuPhos (2), (R,R)-i-Pr-DuPhos (3), or (R,R)-Me-BPE (4); X = BF4 or OTf) with high diastereoselectivity as single C2-symmetric diastereomers. Deprotonation of 2-4 with NaN(SiMe3)2 yielded phosphine-phosphido chelates Rh(diphos)(IsHPCH2PIs) 5-7 with high diastereoselectivity. Thermolysis of 5-7 in toluene at 90 °C caused isomerization to give Rh(diphos)(IsMeP-PIs) (8-10) as mixtures of diastereomers. Under catalytic conditions, Rh-DuPhos precursors slowly converted 1 to a mixture of diastereomers of its isomer, the unsymmetrical diphosphine IsHP-PMeIs (12). We propose a possible mechanism for the isomerization and discuss its relationship to dehydrocoupling catalysis.
Palladium-catalyzed asymmetric phosphination: Enantioselective synthesis of a P-chirogenic phosphine
Moncarz, Jillian R.,Laritcheva, Natalia F.,Glueck, David S.
, p. 13356 - 13357 (2007/10/03)
The racemic secondary phosphine PH(Me)(Is) (1, Is = 2,4,6-(i-Pr)3C6H2) was coupled with PhI in the presence of NaOSiMe3 and the catalyst Pd((R,R)-Me-Duphos)(Ph)(I) (3) to give P(Ph)(Me)(Is) (2) in up to 78% ee.
