11-Step Total Synthesis of (−)-Maoecrystal V

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11-Step Total Synthesis of (−)-Maoecrystal V

An expedient, practical, and enantioselective route to the highly congested ent-kaurane diterpene maoecrystal V is presented. This route, which has been several years in the making, is loosely modeled after a key pinacol shift in the proposed biosynthesis. Only 11 steps, many of which are strategic in that they build key skeletal bonds and incorporate critical functionalities, are required to a...

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A concise total synthesis of (-)-maoecrystal Z.

The first total synthesis of (-)-maoecrystal Z is described. The key steps of the synthesis include a diastereoselective Ti(III)-mediated reductive epoxide coupling reaction and a diastereoselective Sm(II)-mediated reductive cascade cyclization reaction. These transformations enabled the preparation of (-)-maoecrystal Z in only 12 steps from (-)-γ-cyclogeraniol.

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Synthesis of functionalized maoecrystal V core structures.

Two strategies toward the total synthesis of maoecrystal V (1) culminating in the construction of core structures 2 and 3 are described.

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A concise route to a small family of exotic marine alkaloids known as the araiosamines has been developed, and their absolute configuration has been assigned. The dense array of functionality, high polarity, and rich stereochemistry coupled with equilibrating topologies present an unusual challenge for chemical synthesis and an opportunity for innovation. Key steps involve the use of a new reag...

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Enantioselective Synthesis of (−)-Maoecrystal V by Enantiodetermining C–H Functionalization

The evolution of a program directed at the enantioselective total synthesis of maoecrystal V, a highly modified ent-kauranoid, is described. An early stage chiral auxiliary-directed asymmetric C-H functionalization for the construction of a key benzofuran intermediate enabled the first asymmetric synthesis of the natural enantiomer of maoecrystal V, confirming the assigned stereochemistry. A di...

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ژورنال

عنوان ژورنال: Journal of the American Chemical Society

سال: 2016

ISSN: 0002-7863,1520-5126

DOI: 10.1021/jacs.6b06623