Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization

Davies, Huw M. L.; Liao, Kuangbiao

doi:10.1038/s41570-019-0099-x

Cited by 279 publications

(219 citation statements)

References 119 publications

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“…Dinuclear complexes with a paddlewheel structure show a rich chemistry and different electronic configurations as a consequence of the distribution of the energy levels and the number of electrons in the dimetallic unit [1,2]. Dirhodium complexes and, in particular, the tetracarboxylato derivatives, are among the most important and versatile paddlewheel compounds [1,2], and their reactivity has been explored in several fields such as catalysis [3][4][5][6][7][8][9] or bioinorganic chemistry [10][11][12][13]. The ground state electron configuration for most of these complexes is σ 2 π 4 δ 2 δ* 2 π* 4 for a diamagnetic Rh 2 4+ unit, which, therefore, displays a single metal-metal bond order [1,2].…”

Section: Introductionmentioning

confidence: 99%

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

et al. 2019

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In this article, we describe the preparation of anionic heteronuclear one-dimensional coordination polymers made by dirhodium paddlewheels and tetracyanido-metallatate building blocks. A series of complexes of (PPh4)2n[{Rh2(µ-O2CCH3)4}{M(CN)4}]n (M = Ni (1), Pd (2), Pt (3)) formulae were obtained by reaction of [Rh2(μ-O2CCH3)4] with (PPh4)2[M(CN)4] in a 1:1 or 2:1 ratio. Crystals of 1−3 suitable for single crystal X-ray diffraction were grown by slow diffusion of a dichloromethane solution of the dirhodium complex into a chloroform solution of the corresponding tetracyanido–metallatate salt. Compounds 1 and 2 are isostructural and crystallize in the triclinic P-1 space group, while compound 3 crystallizes in the monoclinic P21/n space group. A detailed description of the structures is presented, including the analysis of the packing of anionic chains and PPh4+ cations.

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Section: Introductionmentioning

confidence: 99%

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

et al. 2019

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“…The use of 2 equiv of HFIP appeared to be the optimum amount and the reaction failed completely when it was carried out neat in HFIP. A range of other related chiral catalysts were examined in this reaction (Table , entries 4–8). Although several gave reasonable levels of enantioselectivity, none outperformed Rh 2 ( S ‐NTTL) 4 .…”

Section: Methodsmentioning

confidence: 99%

“…In the early studies with Rh 2 ( S ‐DOSP) 4 as catalyst, the diazo‐derived donor/acceptor carbenes inserted into the C−H bond which is between oxygen and benzylic/allylic (proximal C−H) position . Recently, our group developed a new generation of bulky dirhodium tetracarboxylate catalysts capable of functionalizing electronically less preferred C−H bonds over more feasible ones . Thus, we envisioned that the reaction of allyl silyl ethers with an appropriate dirhodium carbene system derived from diazo compounds may also lead to selective C−H functionalization at the distal position.…”

Section: Methodsmentioning

confidence: 99%

Distal Allylic/Benzylic C−H Functionalization of Silyl Ethers Using Donor/Acceptor Rhodium(II) Carbenes

2020

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Regio‐ and stereoselective distal allylic/benzylic C−H functionalization of allyl and benzyl silyl ethers was achieved using rhodium(II) carbenes derived from N‐sulfonyltriazoles and aryldiazoacetates as carbene precursors. The bulky rhodium carbenes led to highly site‐selective functionalization of less activated allylic and benzylic C−H bonds even in the presence of electronically preferred C−H bonds located α to oxygen. The dirhodium catalyst Rh2(S‐NTTL)4 is the most effective chiral catalyst for triazole‐derived carbene transformations, whereas Rh2(S‐TPPTTL)4 works best for carbenes derived from aryldiazoacetates. The reactions afford a variety of δ‐functionalized allyl silyl ethers with high diastereo‐ and enantioselectivity. The utility of the present method was demonstrated by its application to the synthesis of a 3,4‐disubstituted l‐proline scaffold.

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“…The properties and reactivity of these complexes and their derivatives make them very interesting compounds for the scientific community. Due to their potential applications, they have been studied in fields like catalysis [ 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 , 12 ], bioinorganic chemistry [ 13 , 14 , 15 , 16 , 17 ], metal organic frameworks (MOFs) [ 18 , 19 ], or gas absorption [ 20 , 21 ]. Metal-organic aerogels [ 22 , 23 ] and liquid crystals [ 24 , 25 ] can also be obtained using them as building blocks.…”

Section: Introductionmentioning

confidence: 99%

Heteronuclear Dirhodium-Gold Anionic Complexes: Polymeric Chains and Discrete Units

et al. 2020

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In this article, we report on the synthesis and characterization of the tetracarboxylatodirhodium(II) complexes [Rh2(μ–O2CCH2OMe)4(THF)2] (1) and [Rh2(μ–O2CC6H4–p–CMe3)4(OH2)2] (2) by metathesis reaction of [Rh2(μ–O2CMe)4] with the corresponding ligand acting also as the reaction solvent. The reaction of the corresponding tetracarboxylato precursor, [Rh2(μ–O2CR)4], with PPh4[Au(CN)2] at room temperature, yielded the one-dimensional polymers (PPh4)n[Rh2(μ–O2CR)4Au(CN)2]n (R = Me (3), CH2OMe (4), CH2OEt (5)) and the non-polymeric compounds (PPh4)2{Rh2(μ–O2CR)4[Au(CN)2]2} (R = CMe3 (6), C6H4–p–CMe3 (7)). The structural characterization of 1, 3·2CH2Cl2, 4·3CH2Cl2, 5, 6, and 7·2OCMe2 is also provided with a detailed description of their crystal structures and intermolecular interactions. The polymeric compounds 3·2CH2Cl2, 4·3CH2Cl2, and 5 show wavy chains with Rh–Au–Rh and Rh–N–C angles in the ranges 177.18°–178.69° and 163.0°–170.4°, respectively. A comparative study with related rhodium-silver complexes previously reported indicates no significant influence of the gold or silver atoms in the solid-state arrangement of these kinds of complexes.

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Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization

Cited by 279 publications

References 119 publications

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

Linear One-Dimensional Coordination Polymers Constructed by Dirhodium Paddlewheel and Tetracyanido-Metallate Building Blocks

Distal Allylic/Benzylic C−H Functionalization of Silyl Ethers Using Donor/Acceptor Rhodium(II) Carbenes

Heteronuclear Dirhodium-Gold Anionic Complexes: Polymeric Chains and Discrete Units

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