General synthesis of P-stereogenic compounds: the menthyl phosphinate approach. Issue 31 (20th July 2016)

• Record Type: Journal Article
• Authors: Berger, Olivier; Montchamp, Jean-Luc
• Is Part Of: Organic & biomolecular chemistry. Volume 14:Issue 31(2016)
• Page Start: 7552
• Page End: 7562
• Publication Date: 2016-07-20
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/c6ob01413e
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Easily prepared menthyl phosphinates of high diastereoisomeric purity provide versatile intermediates for the synthesis of P -stereogenic compounds. Abstract : Easily prepared menthyl phosphinates of high diastereoisomeric purity provide versatile intermediates for the synthesis of P -stereogenic compounds. Previous efforts starting about fifty years ago have been hampered by a lack of generality so the menthyl route has been nearly abandoned. Herein we provide a general solution to this long-standing problem and describe a general synthesis of menthyl H -phosphinate and disubstituted phosphinate esters. The method to prepare these versatile precursors relies on a simple and inexpensive process avoiding the use of phosphorus trichloride, Grignard reagents, and complicated cryogenic crystallizations. Established protocols can then be employed to synthesize P -stereogenic secondary and tertiary phosphine oxides and therefore P -stereogenic phosphine ligands.