Asymmetric hydroarsination reactions toward synthesis of alcohol functionalised C-chiral As-P ligands promoted by chiral cyclometallated complexes

Yuen Lin Cheow, Sumod A. Pullarkat, Yongxin Li, Pak Hing Leung

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12 Citations (Scopus)


The asymmetric hydroarsination reactions between diphenylarsine and 3-diphenylphosphanyl-but-3-en-1-ol and 2-diphenylphosphanyl-prop-2-en-1-ol have been achieved using the organopalladium complex containing ortho-metallated (R)-[1-(dimethylamino)ethylnaphthalene as the chiral reaction template in high stereoselectivities under mild conditions. Hydroarsination of 3-diphenylphosphanyl-but-3-en-1-ol with diphenylarsine generated only one stereoisomer as five-membered As-P bidentate chelate on chiral naphthylamine palladium template. Using the same chiral metal template, similar hydroarsination reaction was carried out on 2-diphenylphosphanyl-prop-2-en-1-ol which gave two different products in the ratio of 2.6 to 1. The major isomer was identified as the expected five-membered As-P bidentate ligand and the minor isomer was identified as the elimination product. The naphthylamine auxiliary could be removed chemoselectively by treatment with concentrated hydrochloric acid. Optically pure As-P ligands containing the hydroxy groups at the chiral carbon centres were prepared by ligand displacement. The absolute configuration and coordination properties of the complexes have been established by single crystal X-ray analysis.

Original languageEnglish
Pages (from-to)4215-4220
Number of pages6
JournalJournal of Organometallic Chemistry
Issue number26
Publication statusPublished - 1 Jan 2012
Externally publishedYes


  • Allylic phosphine
  • Asymmetric hydroarsination
  • Chiral P-As ligand
  • Palladacycle

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