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Benincori T, Brenna E, Sannicolò F, et al. New Class of Chiral Diphosphine Ligands for Highly Efficient Transition Metal-Catalyzed Stereoselective Reactions: The Bis(diphenylphosphino) Five-membered Biheteroaryls. J Org Chem. 1996;61(18):6244-6251doi: 10.1021/jo960211f.
Benincori, T., Brenna, E., Sannicolò, F., Trimarco, L., Antognazza, P., Cesarotti, E., Demartin, F., & Pilati, T. (1996). New Class of Chiral Diphosphine Ligands for Highly Efficient Transition Metal-Catalyzed Stereoselective Reactions: The Bis(diphenylphosphino) Five-membered Biheteroaryls. The Journal of organic chemistry, 61(18), 6244-6251. https://doi.org/10.1021/jo960211f
Benincori, Tiziana, et al. "New Class of Chiral Diphosphine Ligands for Highly Efficient Transition Metal-Catalyzed Stereoselective Reactions: The Bis(diphenylphosphino) Five-membered Biheteroaryls." The Journal of organic chemistry vol. 61,18 (1996): 6244-6251. doi: https://doi.org/10.1021/jo960211f
Benincori T, Brenna E, Sannicolò F, Trimarco L, Antognazza P, Cesarotti E, Demartin F, Pilati T. New Class of Chiral Diphosphine Ligands for Highly Efficient Transition Metal-Catalyzed Stereoselective Reactions: The Bis(diphenylphosphino) Five-membered Biheteroaryls. J Org Chem. 1996 Sep 06;61(18):6244-6251. doi: 10.1021/jo960211f. PMID: 11667462.
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J Org Chem. 1996 Sep 06;61(18):6244-6251. doi: 10.1021/jo960211f.

New Class of Chiral Diphosphine Ligands for Highly Efficient Transition Metal-Catalyzed Stereoselective Reactions: The Bis(diphenylphosphino) Five-membered Biheteroaryls.

The Journal of organic chemistry

Tiziana Benincori, Elisabetta Brenna, Franco Sannicolò, Licia Trimarco, Patrizia Antognazza, Edoardo Cesarotti, Francesco Demartin, Tullio Pilati

Affiliations

  1. Dipartimento di Chimica Organica e Industriale, Università di Milano, e Centro CNR Sintesi Stereochimica Speciali Sistemi Organici, Via Golgi 19, I-20133 Milano, Italy, Dipartimento di Chimica Inorganica, Metallorganica e Analitica Università di Milano, e Centro CNR Sintesi e Struttura dei Composti dei Metalli di Transizione nei Bassi Stati di Ossidazione, Via Venezian 21, I-20133 Milano, Italy, Dipartimento di Chimica Strutturale e Stereochimica Inorganica, Università di Milano, Via Venezian 21, I-20133 Milano, Italy, and Centro CNR per lo Studio delle Relazioni fra Struttura e Reattività Chimica, Via Golgi 19, I-20133 Milano, Italy.

PMID: 11667462 DOI: 10.1021/jo960211f

Abstract

The synthesis and application of three examples of a new class of chiral (C(2)) atropisomeric diphosphines characterized by two interconnected five-membered heteroaromatic rings, with hindered rotation around the interanular bond, are described. Optically pure (+)- and (-)-2,2'-bis(diphenylphosphino)-4,4',6,6'-tetramethyl-3,3'-bibenzo[b]thiophene (tetraMe-bitianp) (1a) and the parent unsubstituted system (+)- and (-)-bitianp (1b) were synthesized. They were found to be optically stable at 100 degrees C and were successfully employed as ligands in the Ru(II)-catalyzed hydrogenation of alpha- and beta-oxo esters to the corresponding alpha- and beta-hydroxy esters and in the hydrogenation of olefinic substrates. The optical and chemical yields were comparable with those reported for the same Ru(II)-binap-catalyzed reactions carried out under the same experimental conditions. The 2,2'-bis(diphenylphosphino)-3,3'-bibenzo[b]furan (1c), the oxygenated analogue of bitianp, was found to be configurationally unstable at room temperature. Complete structural X-ray elucidation of the Pd complexes of 1a-c is reported. The advantages of these biheteroaromatic ligands over the classical biaryl systems are discussed.

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