Synthesis of the First

Marie E. Krafft; Yiu-Yin Cheung; Carmelinda A. Juliano-Capucao

doi:10.1055/s-2000-6302

Synthesis 2000; 2000(7): 1020-1026
DOI: 10.1055/s-2000-6302

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Synthesis of the First "Inside-Outside" Eight-Membered Ring via Ring-Closing Metathesis: A Total Synthesis of (±)-Asteriscanolide

Marie E. Krafft^* , Yiu-Yin Cheung, Carmelinda A. Juliano-Capucao

^*Department of Chemistry, Florida State University, Tallahassee, FL 32306, USA

Abstract

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A total synthesis of (±)-asteriscanolide which features two transition metal-mediated carbocyclic ring forming reactions as key elements of our strategy (Scheme 1) is described. The highly functionalized cyclopentenone 4, the product of a cobalt-mediated Pauson-Khand [2 + 2 + 1] cycloaddition, is the key starting point for the synthesis. Excellent regiocontrol was obtained in the intermolecular Pauson-Khand reaction. Further synthetic manipulations of 4 led to diene 16 which underwent ring-closing metathesis using (PPh₃)₂Cl₂Ru(CHPh) to provide the desired "inside-outside" tricycle 17. Conversion of 17 to 1 was achieved in a minimal number of steps. The synthesis of asteriscanolide has been achieved in 19 steps and 12% overall yield.

ring-closing - metathesis - total synthesis - Pauson-Khand cycloaddition - transition metal mediated reactions

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