Synthesis of Cyclic 1,2‐Bisphosphines by Tandem Michael Addition of 2,3‐Bis(diarylphosphinyl)‐1,3‐butadiene

• Published in: European journal of organic chemistry Vol. 26; no. 4
• Main Authors: Chen, Zhenqiang, Sun, Yingying, Wang, Shoufeng, Zhang, Qing‐Wei
• Format: Journal Article
• Language: English
• Published: WEINHEIM Wiley 24.01.2023; Wiley Subscription Services, Inc
• Subjects: asymmetric catalysis; Chemical synthesis; Chemistry; Chemistry, Organic; Coordination compounds; cyclic bisphosphine ligands; Functional groups; metal free reaction; phosphines; Physical Sciences; Science & Technology; transition metal complex; Transition metal compounds; phosphines; transition metal complex; PHOSPHORUS LIGANDS; CATALYSIS; HIGHLY ENANTIOSELECTIVE HYDROGENATION; ASYMMETRIC TRANSFER HYDROGENATION; ACID; RHODIUM COMPLEX; OLEFINS; metal free reaction; asymmetric catalysis; cyclic bisphosphine ligands
• ISSN: 1434-193X; 1099-0690
• DOI: 10.1002/ejoc.202201257

A base‐promoted tandem Michael addition of malonates to 2,3‐ bis(diarylphosphinyl)‐1,3‐butadienes was developed for the synthesis of cyclopentyl 1,2‐bisphosphine compounds. This method enables rapid construction of various 1,2‐bis(diarylphosphinyl)cyclopentanes, and features readily accessible reactants, mild conditions and good functional group tolerance. The product could be easily transformed to the corresponding transition metal complexes, which may find broad applications in asymmetric catalysis. In this work, an efficient method for the synthesis of cyclopentyl 1,2‐diphosphines from malonates and diphosphinyldienes is reported. The asymmetric version was also accomplished in the presence of a chiral auxiliary. The product can be easily converted into a corresponding transition metal complex, which may be widely used in asymmetric catalysis.