金催化的 1,11-二烯-3,9-二炔苯甲酸酯的双环异构化中配体控制的产物选择性。
Ligand-controlled product selectivity in gold-catalyzed double cycloisomerization of 1,11-dien-3,9-diyne benzoates.
机构信息
§Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.
†School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
出版信息
J Am Chem Soc. 2015 May 20;137(19):6350-5. doi: 10.1021/jacs.5b02377. Epub 2015 May 7.
A synthetic method to prepare tricyclic bridged heptenones and hexenones from gold(I)-catalyzed double cycloisomerization of 1,11-dien-3,9-diyne benzoates is described. A divergence in product selectivity was achieved by fine-tuning the steric nature of the ligand of the Au(I) catalyst. In the presence of MeCNAu(JohnPhos)SbF6(-) (JohnPhos = (1,1'-biphenyl-2-yl)-di-tert-butylphosphine) as the catalyst, tandem 1,3-acyloxy migration/metallo-Nazarov cyclization/1,6-enyne addition/Cope rearrangement of the substrate was found to selectively occur to afford the bridged heptenone adduct. In contrast, changing the Au(I) catalyst to MeCNAu(Me4tBuXPhos)SbF6(-) (Me4tBuXPhos = di-tert-butyl(2',4',6'-triisopropyl-3,4,5,6-tetramethyl-[1,1'-biphenyl]-2-yl)phosphine) was observed to result in the 1,11-dien-3,9-diyne benzoate undergoing a more rapid tandem 1,3-acyloxy migration/metallo-Nazarov cyclization/[4 + 2]-cyclization pathway to give the bridged hexenone derivative.
一种从金（I）催化的 1,11-二烯-3,9-二炔苯甲酸酯的双环异构化制备三环桥接庚烯酮和己烯酮的合成方法。通过精细调整 Au（I）催化剂配体的空间性质，可以实现产物选择性的差异。在[MeCNAu（JohnPhos）]（+）SbF6（-）（JohnPhos=（1,1'-联苯-2-基）-二叔丁基膦）作为催化剂的存在下，发现底物的串联 1,3-酰氧基迁移/金属诺扎罗夫环化/1,6-烯炔加成/Cope 重排选择性地发生，得到桥接庚烯酮加合物。相比之下，将 Au（I）催化剂改为[MeCNAu（Me4tBuXPhos）]（+）SbF6（-）（Me4tBuXPhos=二叔丁基（2',4',6'-三异丙基-3,4,5,6-四甲基-[1,1'-联苯]-2-基）膦），观察到 1,11-二烯-3,9-二炔苯甲酸酯经历更快速的串联 1,3-酰氧基迁移/金属诺扎罗夫环化/[4 + 2]-环化途径，得到桥接己烯酮衍生物。
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