Iron-catalysed alkene and heteroarene H/D exchange by reversible protonation of iron-hydride intermediates.
Iron-catalysed alkene and heteroarene H/D exchange by reversible protonation of iron-hydride intermediates.
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DOI：
10.1039/d2sc03802a
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发表时间：
2022-09-14
期刊：
影响因子：
8.4
通讯作者：
中科院分区：
文献类型：
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作者：
C-H官能化反应为分子构建和多样化提供了可持续的方法。然而，这些反应仍然由贵金属催化主导。虽然铁催化的C-H活化反应的显着兴趣已经出现，这些过程的分离，表征和机理的理解仍然缺乏。本文报道了使用CD 3 OD的铁催化的C（sp2）-H键氢/氘交换反应用于杂环和首次用于烯烃（38个实例）。关键的铁-芳基和铁-烯基C-H金属间化合物中间体的分离和表征，包括通过单晶X-射线衍射，为活性氢化铁催化剂的可逆质子化提供了证据。观察到良好的化学选择性为两种底物类。所开发的程序是正交于以前的铁催化的H/D交换方法，其使用C6 D 6，D2，或D2 O作为氘源，并只使用工作台稳定的试剂，包括铁（ii）预催化剂。此外，还报道了一种新的铁氢化物形成机理，其中β-氢化物从醇中消除产生铁氢化物。C-H活化产生的有机金属产物的生产、分离和纯化能力为未来的发现和开发提供了基础。本文报道了铁催化的C（sp2）-H键H/D交换反应。关键的C-H金属间化合物中间体的表征为氢化铁催化剂的可逆质子化提供了证据。
C–H functionalisation reactions offer a sustainable method for molecular construction and diversification. These reactions however remain dominated by precious metal catalysis. While significant interest in iron-catalysed C–H activation reactions has emerged, the isolation, characterisation and mechanistic understanding of these processes remain lacking. Herein the iron-catalysed C(sp2)–H bond hydrogen/deuterium exchange reaction using CD3OD is reported for both heterocycles and, for the first time, alkenes (38 examples). Isolation and characterisation, including by single-crystal X-ray diffraction, of the key iron-aryl and iron-alkenyl C–H metallation intermediates provided evidence for a reversible protonation of the active iron hydride catalyst. Good chemoselectivity was observed for both substrate classes. The developed procedure is orthogonal to previous iron-catalysed H/D exchange methods which used C6D6, D2, or D2O as the deuterium source, and uses only bench-stable reagents, including the iron(ii) pre-catalyst. Further, a new mechanism of iron-hydride formation is reported in which β-hydride elimination from an alcohol generates the iron hydride. The ability to produce, isolate and characterise the organometallic products arising from C–H activation presents a basis for future discovery and development. The iron-catalysed C(sp2)–H bond H/D exchange reaction using CD3OD is reported for both heterocycles and alkenes. Characterisation of the key C–H metallation intermediates provided evidence for reversible protonation of the iron hydride catalyst.
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影响因子：
15
作者：
Garhwal S;Kaushansky A;Fridman N;Shimon LJW;Ruiter G
通讯作者：
Ruiter G
影响因子：
16.6
作者：
Bourriquen, Florian;Rockstroh, Nils;Bartling, Stephan;Junge, Kathrin;Beller, Matthias
通讯作者：
Beller, Matthias
影响因子：
4.6
作者：
Britton, Luke;Docherty, Jamie H.;Thomas, Stephen P.
通讯作者：
Thomas, Stephen P.
影响因子：
15
作者：
Farizyan M;Mondal A;Mal S;Deufel F;van Gemmeren M
通讯作者：
van Gemmeren M
DOI：
10.1039/dt9760001232
发表时间：
1976-01-01
期刊：
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
影响因子：
--
作者：
BELLERBY, JM;MAYS, MJ;SEARS, PL
通讯作者：
SEARS, PL