Asymmetric Synthesis of C2‐Symmetric Axially Chiral Biaryls through Rhodium‐Catalyzed and Alkyne‐Controlled Diastereoselective Double [2+2+2] Cycloaddition. Issue 30 (19th September 2013)

• Record Type: Journal Article
• Authors: Mori, Ayaka; Araki, Tatsuya; Miyauchi, Yuta; Noguchi, Keiichi; Tanaka, Ken
• Is Part Of: European journal of organic chemistry. Issue 30(2013)
• Page Start: 6774
• Page End: 6778
• Publication Date: 2013-09-19
• Subjects: Alkynes -- Axial chirality -- Bi­aryls -- Cycloaddition -- Rhodium; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201300741
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract: The asymmetric synthesis of C 2 ‐symmetric axially chiral biaryls was achieved by the cationic rhodium(I)/1, 3‐bis(diphenylphosphino)propane (dppp) complex catalyzed diastereoselective double [2+2+2] cycloaddition of ( R )‐3‐butyn‐2‐ol‐derived tetraynes with functionalized monoynes. Interestingly, the use of propiolates afforded biaryls possessing large dihedral angles, and in contrast, the use of propargyl alcohol afforded biaryls possessing small dihedral angles. Abstract : A cationic rhodium(I)/1, 3‐bis(diphenylphosphino)propane (dppp) complex catalyzed double [2+2+2] cycloaddition of ( R )‐3‐butyn‐2‐ol‐derived tetraynes with functionalized monoynes affords C 2 ‐symmetric axially chiral biaryls with complete diastereoselectivity. The use of propiolates affords biaryls possessing large dihedral angles, and in contrast, the use of propargyl alcohol affords biaryls possessing small dihedral angles. nbd = norbornadiene.