Calcium-Catalyzed Dehydrogenative Silylation of Aromatic Ethers with Hydrosilane

被引：20
作者：
Zhao, Lanxiao [1 ,2 ]
Shi, Xianghui [1 ]
Cheng, Jianhua [1 ,2 ]
机构：
[1] Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China
[2] Univ Sci & Technol China, Hefei 230029, Anhui, Peoples R China
来源：
ACS CATALYSIS | 2021年 / 11卷 / 04期
基金：
中国国家自然科学基金;
关键词：
calcium complexes; C-H activation; anisole; hydrosilanes; dehydrogenative silylation; HYDRIDE; COMPLEXES;
D O I：
10.1021/acscatal.0c05440
中图分类号：
O64 [物理化学（理论化学）、化学物理学];
学科分类号：
070304 ; 081704 ;
摘要：
The catalytic regioselective C-H silylation of a wide range of alkoxy-substituted benzene derivatives with primary hydrosilane was achieved by the use of scorpionate-supported calcium benzyl complex [(Tp(Ad,iPr))Ca(p-CH2C6H4Me)(THP)] (1) (Tp(Ad,iPr) = hydrotris(3-adamantyl-5-isopropylpyrazolyl)borate, THP = tetrahydropyran) as the precatalyst. This protocol offers an atom-efficient and straightforward method for the synthesis of a variety of silyl-substituted aromatic ether derivatives without a hydrogen acceptor and free of transition metal. Calcium anisyl complexes [(Tp(Ad,iPr))Ca(o-MeO-m-Br-C6H3)] (5) and [(Tp(Ad,iPr))Ca(o-Me-OCH2C6H4)] (6), proposed as the catalytic reaction intermediates, were isolated and structurally characterized.
引用
收藏
页码：2041 / 2046
页数：6
相关论文
共 58 条
[1]   Alkaline Earth-Centered CO Homologation, Reduction, and Amine Carbonylation [J].
Anker, Mathew D. ;
Kefalidis, Christos E. ;
Yang, Yan ;
Fang, Jian ;
Hill, Michael S. ;
Mahon, Mary F. ;
Maron, Laurent .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (29) :10036-10054
[2]   Electrophilic Aromatic Substitution with Silicon Electrophiles: Catalytic Friedel-Crafts C-H Silylation [J].
Baehr, Susanne ;
Oestreich, Martin .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (01) :52-59
[3]   Alkene Transfer Hydrogenation with Alkaline-Earth Metal Catalysts [J].
Bauer, Heiko ;
Thum, Katharina ;
Alonso, Mercedes ;
Fischer, Christian ;
Harder, Sjoerd .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (13) :4248-4253
[4]   Simple Alkaline-Earth Metal Catalysts for Effective Alkene Hydrogenation [J].
Bauer, Heiko ;
Alonso, Mercedes ;
Fischer, Christian ;
Roesch, Bastian ;
Elsen, Holger ;
Harder, Sjoerd .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (46) :15177-15182
[5]   Imine hydrogenation with simple alkaline earth metal catalysts [J].
Bauer, Heiko ;
Alonso, Mercedes ;
Farber, Christian ;
Elsen, Holger ;
Pahl, Jurgen ;
Causero, Andrea ;
Ballmann, Gerd ;
De Proft, Frank ;
Harder, Sjoerd .
NATURE CATALYSIS, 2018, 1 (01) :40-47
[6]   DIRECTED LITHIATION OF AROMATIC TERTIARY AMIDES - AN EVOLVING SYNTHETIC METHODOLOGY FOR POLYSUBSTITUTED AROMATICS [J].
BEAK, P ;
SNIECKUS, V .
ACCOUNTS OF CHEMICAL RESEARCH, 1982, 15 (10) :306-312
[7]   Ligand Effects in Calcium Catalyzed Ketone Hydroboration [J].
Brand, Steffen ;
Causero, Andrea ;
Elsen, Holger ;
Pahl, Juergen ;
Langer, Jens ;
Harder, Sjoerd .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2020, 2020 (18) :1728-1735
[8]   Calcium-Catalyzed Arene C-H Bond Activation by Low-Valent AlI [J].
Brand, Steffen ;
Elsen, Holger ;
Langer, Jens ;
Grams, Samuel ;
Harder, Sjoerd .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2019, 58 (43) :15496-15503
[9]   Calcium stilbene complexes: structures and dual reactivity [J].
Causero, Andrea ;
Elsen, Holger ;
Ballmann, Gerd ;
Escalona, Ana ;
Harder, Sjoerd .
CHEMICAL COMMUNICATIONS, 2017, 53 (75) :10386-10389
[10]   β-Diketiminate calcium hydride complexes: the importance of solvent effects [J].
Causero, Andrea ;
Ballmann, Gerd ;
Pahl, Juergen ;
Faerber, Christian ;
Intemann, Julia ;
Harder, Sjoerd .
DALTON TRANSACTIONS, 2017, 46 (06) :1822-1831
123456