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Synthesis 2008(9): 1460-1466
DOI: 10.1055/s-2008-1067030
DOI: 10.1055/s-2008-1067030
PAPER
© Georg Thieme Verlag Stuttgart · New YorkThe Concise Synthesis of a Key Intermediate for the Total Synthesis of Fumagillin, TNP-470, and Ovalicin
Weitere Informationen
Received
27 December 2007
Publikationsdatum:
16. April 2008 (online)
Publikationsverlauf
Publikationsdatum:
16. April 2008 (online)
Abstract
The facile synthesis of a key intermediate for the total synthesis of the antiangiogenic compound fumagillin, its semisynthetic analogue TNP-470, and ovalicin is described. The methodology employs a Diels-Alder strategy and a zinc-mediated ring-opening reaction to realize the cyclohexane backbone.
Key words
angiogenesis inhibitors - Diels-Alder reaction - syn reduction - dihydroxylation - HIV
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Initially, we isolated the double-bond-reduced product with the PMB group intact and then proceeded with PMB deprotection using DDQ in CH2Cl2/H2O. However, a prolonged reaction time with Pd/C also resulted in the saturated PMB-deprotected product.
20The reaction conditions employed for the attempted protection of the alcohol were (a) TBDPSCl, 1H-imidazole, CH2Cl2; (b) MOMCl, DIPEA, CH2Cl2; (c) BzCl, py, CH2Cl2, and those employed for the attempted ketal deprotection were (a) PTSA (cat.), acetone-H2O; (b) CSA, acetone-H2O; (c) PPTS, acetone-H2O; (d) TMSOTf, CH2Cl2.