The Mechanism of Rhodium-Catalyzed Allylic C-H Amination.

Published on Mar 2, 2020in Journal of the American Chemical Society14.612
· DOI :10.1021/JACS.0C01069
Robert J. Harris2
Estimated H-index: 2
(Emory University),
Jiyong Park14
Estimated H-index: 14
(KAIST)
+ 6 AuthorsSimon B. Blakey20
Estimated H-index: 20
(Emory University)
Sources
Abstract
Herein the mechanism of catalytic allylic C–H amination reactions promoted by Cp*Rh complexes is reported. Reaction kinetics experiments, stoichiometric studies, and DFT calculations demonstrate th...
📖 Papers frequently viewed together
3 Citations
20097.96Chemsuschem
6 Authors (NJ Niek Ronde, ..., Dieter Vogt)
13 Citations
2012
2 Citations
References0
Newest
Cited By17
Newest
#1Yu ShiH-Index: 1
#2Hongli Wu (TJU: Tianjin University)H-Index: 3
Last. Genping HuangH-Index: 17
view all 3 authors...
Density functional theory calculations have been performed to investigate the rhodium(I)/bisoxazolinephosphine-catalyzed amination of allylic carbonates. The computations reveal that after formation of the η3-allyl Rh(III) species via initial C–O oxidative addition, the ensuing C–N bond formation via outer-sphere nucleophilic attack represents the step that determines the regio- and enantioselectivities of the overall reaction. It was found that in the nucleophilic attack transition states, the ...
Source
#1Yulei Wang (GAU: University of Göttingen)H-Index: 1
#2Zhipeng Lin (GAU: University of Göttingen)H-Index: 2
Last. Lutz Ackermann (GAU: University of Göttingen)H-Index: 125
view all 4 authors...
The oxidative intermolecular nitrogenation of C(sp3)-H bonds represents one of the most straightforward strategies to construct nitrogen-containing molecules. However, a sacrificial chemical oxidant is generally required. Herein, we describe electrochemical oxidative intermolecular allylic C(sp3)-H aminations in an undivided cell by electric current. The cross-dehydrogenative amination proceeded efficiently with ample scope under metal- and chemical oxidant-free reaction conditions, giving molec...
Source
#1Deng Pan (DUT: Dalian University of Technology)
#2Gen Luo (Anda: Anhui University)H-Index: 13
Last. Yi Luo (DUT: Dalian University of Technology)H-Index: 26
view all 5 authors...
Computational studies on Ir(III)-catalyzed intermolecular branch-selective allylic C–H amination of terminal olefins with methyl dioxazolone have been carried out to investigate the mechanism, including the origins of regioselectivity and catalytic activity difference. The result suggests that the reaction proceeds through generation of active species, alkene coordination, allylic C–H activation, decarboxylation, migratory insertion, and protodemetalation. The presence of AgNTf2 could thermodyna...
Source
The potential access to Co IV species for promoting transformations that are particularly challenging at Co III still remains underexploited in the context of Cp*Co-catalyzed C-H functionalization reactions. Herein, we disclose a combined experimental and computational strategy for uncovering the intermediacy of Cp*Co IV species in a Cp*Co-mediated C-S bond-reductive elimination. These studies support the intermediacy of high-valent Cp*Co intermediates in C-H functionalization reactions, under o...
3 CitationsSource
Density functional theory calculations have revealed the mechanism and origins of reactivity and regioselectivity of the Cp*Ir(III)/Cp*Rh(III)-catalyzed allylic C–H amidation of alkenes and dioxazolones. Generally, the catalytic cycle consists of alkene coordination, C(sp3)−H activation, dioxazolone oxidative addition, reductive elimination and proto-demetallation to give the final aimdation product. The C–H activation is found to be the rate-determining step, and controls the reactivity of the ...
Source
#1Kuhali DasH-Index: 3
Last. Maji B
view all 3 authors...
Source
#1Supriya RejH-Index: 8
#2Amrita DasH-Index: 2
Last. Naoto ChataniH-Index: 102
view all 3 authors...
Abstract In the field of C–H bond functionalization chemistry, directed C–H bond activation strategies are highly appreciated due to the high efficiency and selectivity of such reactions towards a certain type of C–H bond. Considering extraordinarily rapid progress in directed C–H bond functionalization reactions, we summarize the strategic evolution of directed C–H bond activation chemistry in this review. We feel that this review would be of particular interest to scientists who are interested...
18 CitationsSource
#1Shobhan MondalH-Index: 7
#2Tobias PinkertH-Index: 5
Last. Frank GloriusH-Index: 124
view all 4 authors...
Herein, we report a Cp*IrIII-catalyzed highly regioselective and redox-neutral protocol for the construction of 1,4-enynes from unactivated olefins and bromoalkynes via intermolecular allylic C-H alkynylation. The developed mild reaction conditions tolerate a broad range of common functional groups, even enabling selective alkynylation of allylic C-H bonds in the presence of other prominent directing groups. Mechanistic experiments including the isolation of a catalytically active IrIII-allyl sp...
2 CitationsSource
Last. Eric TanH-Index: 3
view all 5 authors...
The Rh(III)-catalyzed allylic C-H alkynylation of non-activated terminal alkenes leads to linear 1,4-enynes at room-temperature. The catalytic system tolerates a wide range of functional groups without competing functionalization at other positions. Similarly, the vinylic C-H alkynylation of α,β- and β,γ- unsaturated amides gives conjugated Z-1,3-enynes and E-enediynes.
2 CitationsSource
#1Shobhan MondalH-Index: 7
#2Tobias PinkertH-Index: 5
Last. Frank GloriusH-Index: 124
view all 4 authors...
Source