10273-90-2Relevant articles and documents
Orthogonal cross-coupling through intermolecular metathesis of unstrained C(aryl)–C(aryl) single bonds
Zhu, Jun,Zhang, Rui,Dong, Guangbin
, p. 836 - 842 (2021)
While metathesis reactions involving carbon–carbon double bonds, namely olefin metathesis, have been well established with broad utility in organic synthesis and materials science, direct metathesis of kinetically less accessible C–C single bonds is extremely rare. Here we report a ruthenium-catalysed reversible C–C single-bond metathesis reaction that allows redox- and pH-neutral biaryl synthesis. Assisted by directing groups, unstrained homo-biaryl compounds undergo aryl exchanges to generate cross-biaryl products, catalysed by a well-defined air-stable ruthenium(II) complex. Functional groups reactive under typical cross-coupling reactions, such as halogen, silyl and boronate moieties, are compatible under the metathesis conditions. Mechanistic studies disclose an intriguing ‘olefin-metathesis-like’ pathway that involves an unexpected heptacoordinated, 18-electron closed-shell intermediate. The distinct reaction mode discovered here is expected to inspire the development of more general C–C single-bond metathesis and orthogonal cross-coupling reactions. [Figure not available: see fulltext.].
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Padwa,Kamigata
, p. 789 (1975)
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Bis[ N, N ′-(2-indanolyl)]-1,5-diazacyclooctane as Unique Metal Ligand: Self-Assembly of Palladium Nanoparticles and Catalytic Reactivity on C-C Bond Formation
Fujiki, Katsumasa,Tanaka, Katsunori
, p. 1097 - 1104 (2018)
A previously unreported 1,5-diazacyclooctane-palladium(II) complex was synthesized using bis[ N, N ′-(2-indanolyl)]-1,5-diazacyclooctane, which was readily prepared via a novel [4+4] homocyclization of the unsaturated imine intermediate generated from acrolein and 1-amino-2-indanol. Interestingly, the 1,5-diazacyclooctane-palladium(II) complex self-assembled to form palladium nanoparticles. This approach readily provided palladium nanoparticles simply by heating a mixture of palladium(II) acetate and bis[ N, N ′-(2-indanolyl)]-1,4-diazacyclooctane in dichloroethane at mild temperatures. The 1,5-diazacyclooctane-derivative-palladium nanoparticles were successfully deployed in synthetic applications as a heterogeneous catalyst, facilitating Suzuki coupling and a challenging C-C bond formation via C(sp 3)-H activation under low catalyst loading conditions.
Enabling Catalytic Arene C-H Amidomethylation via Bis(tosylamido)methane as a Sustainable Formaldimine Releaser
Li, Zhong-Yuan,Chaminda Lakmal, Hetti Handi,Cui, Xin
, p. 3735 - 3740 (2019)
Addition of catalytic arene C-H to formaldimines has been enabled by Ru(II)-catalyzed amidomethylation with bis(tosylamido)methane as a catalytic formaldimine releaser. The new process provides an atom-efficient and sustainable solution to address the challenges of formaldimines in this type of transformation. Furthermore, new synthetic routes based on this catalytic system have been developed for step-efficient access to N-heterotricyclic core structures that are pharmaceutically relevant.
A Graphene Oxide Nanosheet Supported NHC-Palladium Complex as a Highly Efficient and Recyclable Suzuki Coupling Catalyst
Qian, Yingjie,So, Jaeil,Jung, Sang-Yung,Hwang, Sosan,Jin, Myung-Jong,Shim, Sang Eun
, p. 2287 - 2292 (2019)
A practical heterogeneous catalyst was prepared by anchoring a triazine-tethered N-heterocyclic carbene (NHC)-palladium complex on the surface of graphene oxide (GO) nanosheets. The immobilized complex was characterized by X-ray photoelectron spectroscopy, field-emission transmission electron microscopy, energy-dispersive X-ray spectroscopy, and surface area analysis. It proved to be a highly active and durable heterogeneous catalyst for Suzuki coupling reactions. At room temperature, the use of this catalyst enabled the preparation of various biaryls and heterobiaryls in short reaction times. The catalytic system could be recycled at least 10 times with almost consistent activity. The results reveal that the stable palladium complex is strongly anchored on the surface of GO nanosheets. Interestingly, an open planar network of the GO nanosheet support plays a role during the catalytic process in enhancing the catalytic activity.
Transition-Metal-Free Desulfinative Cross-Coupling of Heteroaryl Sulfinates with Grignard Reagents
Wei, Jun,Liang, Huamin,Ni, Chuanfa,Sheng, Rong,Hu, Jinbo
supporting information, (2019/02/05)
A mild cross-coupling reaction of heteroaryl sulfinates with Grignard reagents has been developed under transition-metal-free conditions. This study provides an example of the SO22- as a leaving group in an aromatic system and an effective methodology for the construction of C-C bond.
