Suzuki-Miyaura cross-coupling of aryl carbamates and sulfamates: experimental and computational studies.
Suzuki-Miyaura cross-coupling of aryl carbamates and sulfamates: experimental and computational studies.
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DOI：
10.1021/ja200398c
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发表时间：
2011-04-27
影响因子：
15
通讯作者：
Garg, Neil K.
中科院分区：
文献类型：
--
作者：
Quasdorf, Kyle W.;Antoft-Finch, Aurora;Liu, Peng;Silberstein, Amanda L.;Komaromi, Anna;Blackburn, Tom;Ramgren, Stephen D.;Houk, K. N.;Snieckus, Victor;Garg, Neil K.
首次报道了合成多用途的O-芳基氨基甲酸酯和O-氨基磺酸酯基团的Suzuki-Miyaura交叉偶联反应。该转化利用廉价的、工作台稳定的催化剂NiCl 2（PCy 3）2以良好至优异的产率提供联芳基化合物。这一方法的广泛适用范围已得到证明。除了具有邻位取代基的那些之外，具有供电子和吸电子基团（EDG，EWG）的底物是耐受的。此外，杂芳基底物可以用作偶联配偶体。描述了为这些交叉偶联反应提供完整催化循环的计算研究。与氨基甲酸酯和氨基磺酸酯的氧化加成通过五中心过渡态发生，导致Ar-O键的排他性断裂。发现水稳定Ni-氨基甲酸酯催化剂静止状态，并因此提供氨基甲酸酯偶联速率相对降低的合理化。几个合成的应用，展示了实用的方法在天然产物和生物活性分子的兴趣的多取代芳香族化合物的合成。
The first Suzuki–Miyaura cross-coupling reactions of the synthetically versatile O-aryl carbamate and O-sulfamate groups is described. The transformations utilize the inexpensive, bench-stable catalyst NiCl2(PCy3)2 to furnish biaryls in good to excellent yields. A broad scope for this methodology has been demonstrated. Substrates with electron-donating and electron-withdrawing groups (EDGs, EWGs) are tolerated, in addition to those that possess ortho substitutents. Furthermore, heteroaryl substrates may be employed as coupling partners. A computational study providing the full catalytic cycles for these cross-coupling reactions is described. The oxidative additions with carbamates and sulfamates occur via a five-centered transition state, resulting in the exclusive cleavage of the Ar–O bond. Water is found to stabilize the Ni–carbamate catalyst resting state, and thus provides rationalization of the relative decreased rate of coupling of carbamates. Several synthetic applications are presented to showcase the utility of the methodology in the synthesis of polysubstituted aromatic compounds of natural product and bioactive molecule interest.
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影响因子：
5.2
作者：
Bhayana B;Fors BP;Buchwald SL
通讯作者：
Buchwald SL
影响因子：
2.3
作者：
Braga, Ataualpa A. C.;Morgon, Nelson H.;Maseras, Feliu
通讯作者：
Maseras, Feliu
影响因子：
15
作者：
Braga, AAC;Morgon, NH;Maseras, F
通讯作者：
Maseras, F
影响因子：
4.4
作者：
BECKE, AD
通讯作者：
BECKE, AD
影响因子：
16.6
作者：
Dankwardt, JW
通讯作者：
Dankwardt, JW