Total Synthesis of (−)-Cylindrocyclophanes A and F Exploiting the Reversible Nature of the Olefin Cross Metathesis Reaction

Citations Over TimeTop 10% of 2001 papers

Abstract

Efficient total syntheses of the C(2)-symmetric (-)-cylindrocyclophanes A and F (1a and 1f) have been achieved. The initial strategy featured the use of a common advanced intermediate to assemble in stepwise fashion the required macrocycle of 1f, exploiting in turn a Myers reductive coupling followed by ring-closing metathesis. In a second-generation strategy, a remarkable cross olefin metathesis dimerization cascade was discovered and exploited to assemble the requisite [7,7]-paracyclophane macrocycles of both 1a and 1f from dienyl monomers. The successful syntheses also featured the effective use of the Danheiser annulation to construct substrates for both the Myers reductive coupling and the metathesis dimerizations strategies. Finally, the Kowalski two-step chain homologation of esters to siloxyalkynes proved superior over the original one-step protocol.

Related Papers

• → Ruthenium olefin metathesis catalysts bearing two bulky and unsymmetrical NHC ligands(2022)2 cited
• → The Application of Olefin Metathesis to the Synthesis of Biologically Active Macrocyclic Agents(2005)32 cited
• → Exploring the Ring-Closing Metathesis for the Construction of the Solomonamide Macrocyclic Core: Identification of Bioactive Precursors(2018)15 cited
• → Profluorescent substrates for the screening of olefin metathesis catalysts(2015)6 cited
• → ChemInform Abstract: Olefin Metathesis by Molybdenum Imido Alkylidene Catalysts(1999)