Biomimetic total synthesis of gambogin and rate acceleration of pericyclic reactions in aqueous media

被引:69
作者
Nicolaou, KC
Xu, H
Wartmann, M
机构
[1] Scripps Res Inst, Dept Chem, La Jolla, CA 92037 USA
[2] Scripps Res Inst, Skaggs Inst Chem Biol, La Jolla, CA 92037 USA
[3] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA
关键词
Claisen rearrangement; Diels-Alder reaction; natural products; rate acceleration; total synthesis;
D O I
10.1002/anie.200462211
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A significant rate acceleration of a Claisen rearrangement and of a Claisen/Diels-Alder reaction cascade sequence was observed in the presence of water. This reaction sequence was used in a total synthesis of gambogin (1) from a tricyclic dialkene 3 via 2.
引用
收藏
页码:756 / 761
页数:6
相关论文
共 70 条
[11]   THE MONOFUNCTIONAL CHORISMATE MUTASE FROM BACILLUS-SUBTILIS - STRUCTURE DETERMINATION OF CHORISMATE MUTASE AND ITS COMPLEXES WITH A TRANSITION-STATE ANALOG AND PREPHENATE, AND IMPLICATIONS FOR THE MECHANISM OF THE ENZYMATIC-REACTION [J].
CHOOK, YM ;
GRAY, JV ;
KE, HM ;
LIPSCOMB, WN .
JOURNAL OF MOLECULAR BIOLOGY, 1994, 240 (05) :476-500
[12]   SYNTHESIS AND CLAISEN REARRANGEMENT OF ALKOXYALLYL ENOL ETHERS - EVIDENCE FOR A DIPOLAR TRANSITION-STATE [J].
COATES, RM ;
ROGERS, BD ;
HOBBS, SJ ;
PECK, DR ;
CURRAN, DP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (04) :1160-1170
[13]  
DESIRAJU GR, 1999, WEAK HYDROGEN BOND S, pCH1
[14]   ENERGY SURFACES OF SIGMATROPIC SHIFTS [J].
GAJEWSKI, JJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1980, 13 (05) :142-148
[15]   ALIPHATIC CLAISEN REARRANGEMENT TRANSITION-STATE STRUCTURE FROM SECONDARY ALPHA-DEUTERIUM ISOTOPE EFFECTS [J].
GAJEWSKI, JJ ;
CONRAD, ND .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (10) :2747-2748
[16]   ON THE MECHANISM OF REARRANGEMENT OF CHORISMIC ACID AND RELATED-COMPOUNDS [J].
GAJEWSKI, JJ ;
JURAYJ, J ;
KIMBROUGH, DR ;
GANDE, ME ;
GANEM, B ;
CARPENTER, BK .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (04) :1170-1186
[17]   The Claisen rearrangement. Response to solvents and substituents: The case for both hydrophobic and hydrogen bond acceleration in water and for a variable transition state [J].
Gajewski, JJ .
ACCOUNTS OF CHEMICAL RESEARCH, 1997, 30 (05) :219-225
[18]  
Ganem B., 1996, ANGEW CHEM INT EDIT, V35, P936, DOI [DOI 10.1002/ANIE.199609361, 10.1002/anie.199609361, 10.1002/anie.19960936]
[19]  
Ganem B., 1996, ANGEW CHEM, V108, P1014
[20]   IMPROVED SYNTHESIS OF ARYL 1,1-DIMETHYLPROPARGYL ETHERS [J].
GODFREY, JD ;
MUELLER, RH ;
SEDERGRAN, TC ;
SOUNDARARAJAN, N ;
COLANDREA, VJ .
TETRAHEDRON LETTERS, 1994, 35 (35) :6405-6408