TY - JOUR
T1 - Total Synthesis of Hamigerans and Analogues Thereof. Photochemical Generation and Diels-Alder Trapping of Hydroxy-o-quinodimethanes
AU - Nicolaou, K. C.
AU - Gray, David L.F.
AU - Tae, Jinsung
N1 - Copyright:
Copyright 2008 Elsevier B.V., All rights reserved.
PY - 2004/1/21
Y1 - 2004/1/21
N2 - A number of naturally occurring substances, including hamigerans, contain ring systems which are fused to an aromatic nucleus. A general and streamlined method for the construction of such benzannulated bi- and polycyclic carbon frameworks has been developed, and its scope and limitations were explored. On the basis of the photoenolization of substituted benzaldehydes and subsequent Diels-Alder (PEDA) trapping of the generated hydroxy-o-quinodimethanes, this method was optimized to set the stage for the total synthesis of several naturally occurring members of the hamigeran class. Specifically, the developed synthetic technology served as the centerpiece process for the successful asymmetric synthesis of hamigerans A (2), B (3), and E (7). In addition to the PEDA reactions, several other novel reaction processes are described, including a high-yielding decarbonylative ring contraction and an oxidative decarboxylation of a hydroxyl β-keto ester to afford an α-diketone. A number of analogues of these biologically active natural products were also prepared by application of the developed technology.
AB - A number of naturally occurring substances, including hamigerans, contain ring systems which are fused to an aromatic nucleus. A general and streamlined method for the construction of such benzannulated bi- and polycyclic carbon frameworks has been developed, and its scope and limitations were explored. On the basis of the photoenolization of substituted benzaldehydes and subsequent Diels-Alder (PEDA) trapping of the generated hydroxy-o-quinodimethanes, this method was optimized to set the stage for the total synthesis of several naturally occurring members of the hamigeran class. Specifically, the developed synthetic technology served as the centerpiece process for the successful asymmetric synthesis of hamigerans A (2), B (3), and E (7). In addition to the PEDA reactions, several other novel reaction processes are described, including a high-yielding decarbonylative ring contraction and an oxidative decarboxylation of a hydroxyl β-keto ester to afford an α-diketone. A number of analogues of these biologically active natural products were also prepared by application of the developed technology.
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U2 - 10.1021/ja030498f
DO - 10.1021/ja030498f
M3 - Article
C2 - 14719961
AN - SCOPUS:0347087231
VL - 126
SP - 613
EP - 627
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 2
ER -