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Diastereoselective Synthesis of P-Chirogenic and Atropisomeric 2,2'-Bisphosphino-1,1'-binaphthyls Enabled by Internal Phosphine Oxide Directing Groups.
Angew Chem Int Ed Engl. 2020 May 18; 59(21):8153-8159.AC

Abstract

Diphosphine ligands that merge both axial and P-centered chirality may exhibit superior or unique properties. Herein we report the diastereoselective introduction of P-centered chirality at the 2-position of the axially chiral 2'-(phosphine oxide)-1,1'-binaphthyl scaffold. A lithium-bromide exchange reaction of a 2-bromo-2'-(phosphine oxide)-1,1'-binaphthyl and treatment with dichlorophosphines followed by a nucleophilic organometallic reagent afforded unsymmetrical 2-phosphino-2'-(phosphine oxide)-1,1'-binaphthyls with binaphthyl axial chirality and one or two phosphorus stereocenters with a variety of P substituents. The final diastereomerically pure 2,2'-bisphosphino-1,1'-binaphthyls were obtained by reduction of the phosphine oxide directing group. Preliminary results demonstrated that a ligand with this hybrid chirality could induce higher stereoselectivity in the metal-complex-catalyzed asymmetric hydrogenation of a dialkyl ketone.

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Authors+Show Affiliations

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.

Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, Key Laboratory of Physico-Inorganic Chemistry, College of Chemistry and Materials Science, Northwest University, Xi'an, 710127, P. R. China.

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.

State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering, Donghua University, Shanghai, 201620, P. R. China.

Pub Type(s)

Journal Article

Language

eng

PubMed ID

32196883

Citation

Xue, Qingquan, et al. "Diastereoselective Synthesis of P-Chirogenic and Atropisomeric 2,2'-Bisphosphino-1,1'-binaphthyls Enabled By Internal Phosphine Oxide Directing Groups." Angewandte Chemie (International Ed. in English), vol. 59, no. 21, 2020, pp. 8153-8159.

Xue Q, Huo S, Wang T, et al. Diastereoselective Synthesis of P-Chirogenic and Atropisomeric 2,2'-Bisphosphino-1,1'-binaphthyls Enabled by Internal Phosphine Oxide Directing Groups. Angew Chem Int Ed Engl. 2020;59(21):8153-8159.

Xue, Q., Huo, S., Wang, T., Wang, Z., Li, J., Zhu, M., & Zuo, W. (2020). Diastereoselective Synthesis of P-Chirogenic and Atropisomeric 2,2'-Bisphosphino-1,1'-binaphthyls Enabled by Internal Phosphine Oxide Directing Groups. Angewandte Chemie (International Ed. in English), 59(21), 8153-8159. https://doi.org/10.1002/anie.202001561

Xue Q, et al. Diastereoselective Synthesis of P-Chirogenic and Atropisomeric 2,2'-Bisphosphino-1,1'-binaphthyls Enabled By Internal Phosphine Oxide Directing Groups. Angew Chem Int Ed Engl. 2020 May 18;59(21):8153-8159. PubMed PMID: 32196883.

* Article titles in AMA citation format should be in sentence-case

TY - JOUR T1 - Diastereoselective Synthesis of P-Chirogenic and Atropisomeric 2,2'-Bisphosphino-1,1'-binaphthyls Enabled by Internal Phosphine Oxide Directing Groups. AU - Xue,Qingquan, AU - Huo,Shangfei, AU - Wang,Tingyi, AU - Wang,Zeming, AU - Li,Jianli, AU - Zhu,Meifang, AU - Zuo,Weiwei, Y1 - 2020/04/16/ PY - 2020/01/30/received PY - 2020/3/21/pubmed PY - 2020/3/21/medline PY - 2020/3/21/entrez KW - P stereocenters KW - asymmetric synthesis KW - atropisomerism KW - axial-to-point chirality transfer KW - phosphane ligands SP - 8153 EP - 8159 JF - Angewandte Chemie (International ed. in English) JO - Angew Chem Int Ed Engl VL - 59 IS - 21 N2 - Diphosphine ligands that merge both axial and P-centered chirality may exhibit superior or unique properties. Herein we report the diastereoselective introduction of P-centered chirality at the 2-position of the axially chiral 2'-(phosphine oxide)-1,1'-binaphthyl scaffold. A lithium-bromide exchange reaction of a 2-bromo-2'-(phosphine oxide)-1,1'-binaphthyl and treatment with dichlorophosphines followed by a nucleophilic organometallic reagent afforded unsymmetrical 2-phosphino-2'-(phosphine oxide)-1,1'-binaphthyls with binaphthyl axial chirality and one or two phosphorus stereocenters with a variety of P substituents. The final diastereomerically pure 2,2'-bisphosphino-1,1'-binaphthyls were obtained by reduction of the phosphine oxide directing group. Preliminary results demonstrated that a ligand with this hybrid chirality could induce higher stereoselectivity in the metal-complex-catalyzed asymmetric hydrogenation of a dialkyl ketone. SN - 1521-3773 UR - https://www.unboundmedicine.com/medline/citation/32196883/Diastereoselective_Synthesis_of_P_Chirogenic_and_Atropisomeric_22'_Bisphosphino_11'_binaphthyls_Enabled_by_Internal_Phosphine_Oxide_Directing_Groups_ DB - PRIME DP - Unbound Medicine ER -