Palladium Complexes Based on Ylide‐Functionalized Phosphines (YPhos): Broadly Applicable High‐Performance Precatalysts for the Amination of Aryl Halides at Room Temperature
Palladium Complexes Based on Ylide‐Functionalized Phosphines (YPhos): Broadly Applicable High‐Performance Precatalysts for the Amination of Aryl Halides at Room Temperature
复制标题
基于叶立德功能化膦（YPhos）的钯配合物：广泛适用的高性能预催化剂，用于芳基卤化物在室温下的胺化
作者：
Jens Tappen;Ilja Rodstein;Katie McGuire;Angela Großjohann;J. Löffler;Thorsten Scherpf;V. H. Gessner
摘要：制备了钯烯丙基、肉桂基和茚基配合物，并与酰基取代的磷化氢Cy3P+−C−(R)PCy2 （R =Me （L1）或Ph (L2)）和Cy3P+−C−(Me)PtBu2 （L3）配合物作为C−N偶联反应的预催化剂。该配合物在4‐氯甲苯与一系列不同胺的胺化反应中具有高活性。与原位生成催化剂相比，预催化剂的产率更高。配体结构的改变允许通过关闭β -氢化物消除或二氮化反应来提高选择性。特别地，基于L2 （joYPhos）的配合物显示出是各种胺和芳基卤化物的通用预催化剂。在室温下，完全转化为所需产物的时间大多在1小时内，从而使L2成为C−N偶联反应中最有效的配体之一。结果表明，该催化剂适用于芳烃氯化物、溴化物、碘化物以及叔芳基胺和仲芳基胺，包括克级应用，催化剂负载低至0.05 mol %。动力学研究进一步证明了TOF大于10,000 h−1的预催化剂具有优异的活性。
Abstract Palladium allyl, cinnamyl, and indenyl complexes with the ylide‐substituted phosphines Cy3P+−C−(R)PCy2 (with R=Me (L1) or Ph (L2)) and Cy3P+−C−(Me)PtBu2 (L3) were prepared and applied as defined precatalysts in C−N coupling reactions. The complexes are highly active in the amination of 4‐chlorotoluene with a series of different amines. Higher yields were observed with the precatalysts in comparison to the in situ generated catalysts. Changes in the ligand structures allowed for improved selectivities by shutting down β‐hydride elimination or diarylation reactions. Particularly, the complexes based on L2 (joYPhos) revealed to be universal precatalysts for various amines and aryl halides. Full conversions to the desired products are reached mostly within 1 h reaction time at room temperature, thus making L2 to one of the most efficient ligands in C−N coupling reactions. The applicability of the catalysts was demonstrated for aryl chlorides, bromides and iodides together with primary and secondary aryl and alkyl amines, including gram‐scale applications also with low catalyst loadings of down to 0.05 mol %. Kinetic studies further demonstrated the outstanding activity of the precatalysts with TOF over 10.000 h−1.
登录
查看更多内容
影响因子：
18.3
作者：
Martin, Ruben;Buchwald, Stephen L.
通讯作者：
Buchwald, Stephen L.
快速激活铃木 - 米龙和芳基酯的布赫瓦尔德 - 哈特维格耦合的PD-催化剂。
DOI：
10.1021/acs.joc.7b02588
发表时间：
2018-01-05
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Dardir AH;Melvin PR;Davis RM;Hazari N;Mohadjer Beromi M
通讯作者：
Mohadjer Beromi M
影响因子：
8.4
作者：
Maiti D;Fors BP;Henderson JL;Nakamura Y;Buchwald SL
通讯作者：
Buchwald SL
DOI：
10.1002/chin.200136081
发表时间：
2001-03
期刊：
The Journal of organic chemistry
影响因子：
--
作者：
Mayssam H. Ali;S. Buchwald
通讯作者：
Mayssam H. Ali;S. Buchwald
影响因子：
5.2
作者：
Melvin PR;Hazari N;Beromi MM;Shah HP;Williams MJ
通讯作者：
Williams MJ