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Development of a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. A unique source of enantioselection in Pd-catalyzed asymmetric construction of quaternary carbons.
J Org Chem. 2005 Sep 02; 70(18):7172-8.JO

Abstract

[reaction: see text] We have recently developed a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. These pentavalent phosphorus compounds have been successfully applied to Pd-catalyzed asymmetric construction of tertiary and quaternary carbons. The actual ligand structure was the trivalent phosphorus species 17, which was generated in situ by BSA-induced P(V) to P(III) transformation of 6, the preligand. Detailed mechanistic studies, including asymmetric amplification and initial rate kinetics, revealed that complex 18 [Pd-17 (1:2) complex] was the active catalyst. The important function of the nitrogen atom on the sidearm in the ligands was also clarified. The source of enantioselection in the construction of asymmetric quaternary carbons was the secondary ligand substrate interaction mediated by N-Zn coordination.

Authors+Show Affiliations

Nemoto T
Graduate School of Pharmaceutical Sciences, Chiba University, Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
Masuda T
No affiliation info available
Matsumoto T
No affiliation info available
Hamada Y
No affiliation info available

MeSH

CarbonCatalysisDrug DesignLigandsMolecular ConformationPalladiumPhosphines

Pub Type(s)

Journal Article
Research Support, Non-U.S. Gov't

Language

eng

PubMed ID

16122235

Citation

Nemoto, Tetsuhiro, et al. "Development of a New Class of Chiral Phosphorus Ligands: P-chirogenic Diaminophosphine Oxides. a Unique Source of Enantioselection in Pd-catalyzed Asymmetric Construction of Quaternary Carbons." The Journal of Organic Chemistry, vol. 70, no. 18, 2005, pp. 7172-8.
Nemoto T, Masuda T, Matsumoto T, et al. Development of a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. A unique source of enantioselection in Pd-catalyzed asymmetric construction of quaternary carbons. J Org Chem. 2005;70(18):7172-8.
Nemoto, T., Masuda, T., Matsumoto, T., & Hamada, Y. (2005). Development of a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. A unique source of enantioselection in Pd-catalyzed asymmetric construction of quaternary carbons. The Journal of Organic Chemistry, 70(18), 7172-8.
Nemoto T, et al. Development of a New Class of Chiral Phosphorus Ligands: P-chirogenic Diaminophosphine Oxides. a Unique Source of Enantioselection in Pd-catalyzed Asymmetric Construction of Quaternary Carbons. J Org Chem. 2005 Sep 2;70(18):7172-8. PubMed PMID: 16122235.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Development of a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. A unique source of enantioselection in Pd-catalyzed asymmetric construction of quaternary carbons. AU - Nemoto,Tetsuhiro, AU - Masuda,Takamasa, AU - Matsumoto,Takayoshi, AU - Hamada,Yasumasa, PY - 2005/8/27/pubmed PY - 2006/5/25/medline PY - 2005/8/27/entrez SP - 7172 EP - 8 JF - The Journal of organic chemistry JO - J Org Chem VL - 70 IS - 18 N2 - [reaction: see text] We have recently developed a new class of chiral phosphorus ligands: P-chirogenic diaminophosphine oxides. These pentavalent phosphorus compounds have been successfully applied to Pd-catalyzed asymmetric construction of tertiary and quaternary carbons. The actual ligand structure was the trivalent phosphorus species 17, which was generated in situ by BSA-induced P(V) to P(III) transformation of 6, the preligand. Detailed mechanistic studies, including asymmetric amplification and initial rate kinetics, revealed that complex 18 [Pd-17 (1:2) complex] was the active catalyst. The important function of the nitrogen atom on the sidearm in the ligands was also clarified. The source of enantioselection in the construction of asymmetric quaternary carbons was the secondary ligand substrate interaction mediated by N-Zn coordination. SN - 0022-3263 UR - https://www.unboundmedicine.com/medline/citation/16122235/Development_of_a_new_class_of_chiral_phosphorus_ligands:_P_chirogenic_diaminophosphine_oxides__A_unique_source_of_enantioselection_in_Pd_catalyzed_asymmetric_construction_of_quaternary_carbons_ DB - PRIME DP - Unbound Medicine ER -