31184-49-3

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Tiglianes such as prostratin and related diterpenoids are biologically significant natural molecules and long-standing targets for organic synthesis community. Due to the complex polycyclic scaffolds, high oxygenation level, and dense functional groups and stereocenters, their de novo chemical syntheses still face formidable challenges despite extensive efforts in the past 40 years. This account details the development of a modular and concise synthesis of prostratin, a potent anti-HIV and anticancer agent. The key approach in this synthesis involved a sequence of oxidative dearomatization and sequential stereoselective installation of peripheral groups to rapidly build the contiguously substituted cyclohexane C-ring. Inspired by Wender's work, an acid- A nd solvent-controlled stereodivergent formation of cyclopropane D-ring was developed. Mechanistic investigations by computational methods revealed that the competition between intra- A nd intermolecular hydrogen bonding led to different conformations, thus favoring different protonation processes. The designed and unexpected chemistry along this campaign reflected the uniqueness of the natural structures and should be amenable to future chemical syntheses of related complex polycyclic molecules.

The invention discloses a method for quickly based on substituted cyclobutanol oxidation open-loop/cyclization reaction preparation Tetralone derivatives of the method, the method is that the aryl substituted cyclobutanol cerium amine in the nitric acid oxidation of a pot of reaction under the action of the generating Tetralone derivatives; this method has the advantages of fast response (30 seconds in the completion of the reaction), the operation is simple (the open reaction), mild reaction conditions, one-step reaction, does not need to use noble metal catalytic, the yield is high, can be expands the quantity reaction and the like, overcome in the prior art long reaction time, requires the use of a noble metal catalyst, more reaction steps, more byproducts and the like. (by machine translation)

A mild and practical tandem oxidative ring-opening/cyclization reaction mediated by Ce4+ for the synthesis of 1-tetralones is presented. This rapid transformation was completed within 30 s and conducted in an open reactor at 0 °C in a water-acetonitrile mixture. Various cyclobutanol derivatives are transformed into desired products in good to high yields, and this reaction can be easily scaled up to the gram scale.

A mild and practical tandem oxidative ring-opening/cyclization reaction mediated by Ce4+ for the synthesis of 1-tetralones is presented. This rapid transformation was completed within 30 s and conducted in an open reactor at 0 °C in a water-acetonitrile mixture. Various cyclobutanol derivatives are transformed into desired products in good to high yields, and this reaction can be easily scaled up to the gram scale.

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