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Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore.
Beilstein Journal of Organic Chemistry ( IF 2.2 ) Pub Date : 2020-05-25 , DOI: 10.3762/bjoc.16.98
Esteban P Urriolabeitia 1 , Pablo Sánchez 1 , Alexandra Pop 2 , Cristian Silvestru 2 , Eduardo Laga 1 , Ana I Jiménez 1 , Carlos Cativiela 1
Affiliation  

The stereoselective synthesis of truxillic bis-amino esters from polyfunctional oxazolones is reported. The reaction of 4-((Z)-arylidene)-2-(E)-styryl-5(4H)-oxazolones 2 with Pd(OAc)2 resulted in ortho-palladation and the formation of a dinuclear open-book complexes 3 with carboxylate bridges, where the Pd atom is C^N bonded to the oxazolone. In 3 the two exocyclic C=C bonds of the oxazolone are in a face-to-face arrangement, which is optimal for their [2 + 2] photocycloaddition. Irradiation of dimers 3 in CH2Cl2 solution with blue light (465 nm) promoted the chemo- and stereoselective [2 + 2] photocycloaddition of the exocyclic C=C bonds and the formation of cyclobutane-containing ortho-palladated complexes 4. Treatment of 4 with CO in a MeOH/NCMe mixture promoted the methoxycarbonylation of the palladated carbon and the release of the corresponding ortho-functionalized 1,3-diaminotruxillic bis-amino esters 5 as single isomers.

中文翻译:

通过Pd介导的Kaede蛋白发色团类似物的光环加成反应合成二氨基truxillic bis-氨基酸的酯。

据报道,由多官能恶唑酮立体合成合成木耳二氨基酯。4-((Z)-亚芳基)-2-(E)-styryl-5(4 H)-恶唑酮2与Pd(OAc)2的反应导致邻位pal合并形成双核开卷复合物带有羧酸盐桥的3,其中Pd原子是与恶唑酮键合的C ^ N。在3中,恶唑酮的两个环外C = C键面对面排列,这对于它们的[2 + 2]光环加成是最佳的。在CH 2 Cl 2中辐照二聚体3蓝光(465 nm)的溶液促进了环外C = C键的化学和立体选择[2 + 2]光环加成反应,并形成了含环丁烷的钯配合物4。在MeOH / NCMe混合物中用CO处理4促进了钯化的碳的甲氧基羰基化,并释放了作为单一异构体的相应的官能化的1,3-二氨基苯甲基双氨基酯5
更新日期:2020-05-25
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