Novel concepts in directed biaryl synthesis, part 101. The lactone concept-a novel approach to the metal-assisted atroposelective construction of axially chiral biaryl systems

被引:75
作者
Bringmann, G
Breuning, M
Pfeifer, RM
Schenk, WA
Kamikawa, K
Uemura, M
机构
[1] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
[2] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany
[3] Osaka Prefecture Univ, Fac Integrated Arts & Sci, Dept Chem, Osaka 5998531, Japan
关键词
biaryls; stereoselective synthesis; atropisomers; axial chirality; ring opening; dynamic kinetic resolution;
D O I
10.1016/S0022-328X(02)01804-1
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The atroposelective synthesis of axially chiral biaryls via configurationally unstable, lactone-bridged biaryls is reviewed. These key molecules are easily accessible by regioselective intramolecular cross-coupling of ester-linked, even sterically hindered aromatic portions and can be cleaved highly atropo-enantio- or -diastereoselectively by three principal options, either (a) by using a wide range of chiral metalated nucleophiles (usually with external asymmetric induction), (b) after Lewis acid activation of the lactone C=O function using uncharged chiral or achiral nucleophiles, or (c) with internal asymmetric induction, using the stereoelement of planar chirality originating from eta(6)-coordination (typically involving Cr or Ru complexes). The resulting ring-opened configurationally stable biaryls are obtained in mostly excellent chemical and optical yields. By the choice of the respective enantiomer of the nucleophile, the method allows the atropo-divergent synthesis of both atropisomers from the same immediate biaryl precursor and, if required, a recycling of the undesired minor atropisomer is possible, too. Such advantages are otherwise well-known for the stereoselective preparation of centrochiral compounds. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:31 / 47
页数:17
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