Pentamethylcyclopentadienyl rhodium(III)-chiral disulfonate hybrid catalysis for enantioselective C-H bond functionalization

• Satake, Shun

• Kurihara, Takumaru

• Nishikawa, Keisuke

• Mochizuki, Takuya

• Hatano, Manabu

• Ishihara, Kazuaki

• Yoshino, Tatsuhiko

• Matsunaga, Shigeki

Abstract

Though Cp*Rh(III) complexes are prominent and versatile catalysts for C-H bond functionalization reactions, catalytic stereocontrol is difficult due to the lack of vacant coordination sites. Here, we report a hybrid strategy for inducing chirality without using previously reported chiral Cp-x ligands. A preformed hybrid catalyst, [Cp*RhLN][6,6'-Br-(S)-BINSate], catalysed C-H activation and subsequent conjugate addition of 2-phenylpyridine derivatives to enones in good yield and enantioselectivity (enantiomeric ratio up to 95:5). In addition to 2-phenylpyridines, the conjugate addition of 6-arylpurines proceeded with an enantiomeric ratio of up to 91:9 using [Cp*RhLN](R)-SPISate]. The results demonstrate that a chiral organic anion can efficiently control the enantioselectivity of Cp*Rh(III)-catalysed C-H bond functionalization without a chiral Cp-x ligand.

Journal

• Nature Catalysis

  Nature Catalysis 1 (8), 585-591, 2018-08

  Nature Publishing Group

Keywords

• Process Chemistry and Technology
• Biochemistry
• Bioengineering
• Catalysis

Details

• CRID: 1050282814039038080
• NII Article ID: 120006709286
• DOI: 10.1038/s41929-018-0106-5
• HANDLE: 2115/75059
• ISSN: 25201158
• Web Site: https://www.nature.com/articles/s41929-018-0106-5
• Web Site: https://www.nature.com/articles/s41929-018-0106-5.pdf
• Text Lang: en
• Article Type: journal article
• Data Source:
  • IRDB
  • Crossref
  • CiNii Articles
  • KAKEN