Discovery of new function of organophosphorus compounds and their applications to catalytic asymmetric synthesis

2013 Fiscal Year Final Research Report

• Project/Area Number: 24659002
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Single-year Grants
• Research Field: Chemical pharmacy
• Research Institution: Chiba University
• Principal Investigator: HAMADA Yasumasa 千葉大学, 薬学研究科(研究院), 教授 (90117846)
• Project Period (FY): 2012-04-01 – 2014-03-31
• Keywords: anionic ligand / phenyl phosphine / phosphide / disproportionation / sulfur / phosphorus / new reaction / tosyl chloride

Research Abstract

We focused on phosphide compounds like a sulfonamide as a precursor of an anionic ligand, which have never been reported to date. We first examined the reaction of phenyl phosphine. But no phosphide was obtained. Then, we examined the experiments to corroborate the known procedure using diphenylphosphine and tosyl chloride. Surprisingly, we obtained tolylthiooxydiphenylphosphine oxide instead of the expected phosphide. Based on the results, we re-examined the reaction of phenylphosphine with tosyl chloride, which afforded phenylthiophosphonic acid phenyl thioester. Interestingly, this reaction is a completely new reaction through disproportionation reaction between sulfur and phosphorus. Next, we focused on the reaction of phenyl phosphine with acylating agents. When phosphine borane instead of phosphine, the desired phosphide was isolated as a borane complex. Now we are examining the removal of the borane from the product.