Organocopper‐Triggered Cyclisation of Conjugated Diene‐ynes: Diastereo‐ and Enantioselective Synthesis of Indenes. Issue 16 (20th October 2015)

• Record Type: Journal Article
• Authors: Arif, Tanzeel; Borie, Cyril; Tintaru, Aura; Naubron, Jean‐Valère; Vanthuyne, Nicolas; Bertrand, Michèle P.; Nechab, Malek
• Is Part Of: Advanced synthesis & catalysis. Volume 357:Issue 16/17(2015)
• Page Start: 3611
• Page End: 3616
• Publication Date: 2015-10-20
• Subjects: carbocycles -- chirality -- cuprates -- cyclization -- enynes; Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201500556
• Languages: English
• ISSNs: 1615-4150

Abstract

Abstract: Organocopper reagents react with readily available chiral conjugated diene‐ynes to give indene derivatives bearing two stereogenic centres. The investigation of this original reaction in optically pure series demonstrates that a double transfer of chirality is operating. A stereocontrolled cascade involving SN 2′ followed by carbocupration and conjugate addition reactions accounts for the total recovery of the initial chirality. The scope and limitations of the reaction were investigated. The high diastereofacial discrimination in the cyclisation step allowed the construction of the quaternary stereocentre with excellent dr and ee, with the opposite configuration depending on the E ‐ or Z ‐configuration of the alkene in the starting material. Post‐functionalisation of indenes allowed the synthesis of indanyl derivatives containing four contiguous stereocentres. Abstract :