Base‐Catalyzed Stereoselective 1,6‐Conjugated Addition/Aromatization of P(O)–H Compounds with para‐Quinone Methides

• Published in: European journal of organic chemistry Vol. 2019; no. 20; pp. 3273 - 3282
• Main Authors: Xiong, Biquan, Wang, Gang, Zhou, Congshan, Liu, Yu, Xu, Weifeng, Xu, Wen‐Yuan, Yang, Chang‐An, Tang, Ke‐Wen
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 02.06.2019; Wiley Subscription Services, Inc
• Subjects: Basic oxides; Catalysis; Chemistry; Chemistry, Organic; Nucleophilic addition; Optical activity; Phosphorylation; Physical Sciences; Quinones; Science & Technology; Stereoselectivity; Synthetic methods; Phosphorylation; ACID; DIARYL; ANNULATION; TRIARYLMETHANES; EXPEDIENT ACCESS; Quinones; ESTERS; Synthetic methods; CYANOSILYLATION; EFFICIENT; KEY; Nucleophilic addition
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.201900419

A versatile base‐catalyzed method for the 1,6‐conjugated addition/aromatization of para‐quinone methides with P(O)–H compounds is illustrated. Further studies on this reaction by using optically active H‐phosphinates show that the reaction takes place stereospecifically with retention or inversion of configuration at the phosphorus center. It is a simple way to produce a broad spectrum of functionalized phosphane oxides and phosphinates from basic P(O)–H starting materials. This finding also contributes significantly to the stereosynthesis in the catalysis. A versatile base‐catalyzed 1,6‐conjugated addition/aromatization of P(O)–H compounds with p‐QMs is described. This protocol avoids the use of metal catalysis and air‐sensitive reagents and has a broad substrate scope. The optically active H‐phosphinates could react with p‐QMs stereospecifically with retention (R3 = Ph, mesityl) or inversion (R3 = Bn) of the configuration at the phosphorus center.