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Journal ArticleDOI: 10.1021/JACS.0C13077

Photochemical C-H Activation Enables Nickel-Catalyzed Olefin Dicarbofunctionalization.

04 Mar 2021-Journal of the American Chemical Society (American Chemical Society (ACS))-Vol. 143, Iss: 10, pp 3901-3910
Abstract: Alkenes, ethers, and alcohols account for a significant percentage of bulk reagents available to the chemistry community. The petrochemical, pharmaceutical, and agrochemical industries each consume gigagrams of these materials as fuels and solvents each year. However, the utilization of such materials as building blocks for the construction of complex small molecules is limited by the necessity of prefunctionalization to achieve chemoselective reactivity. Herein, we report the implementation of efficient, sustainable, diaryl ketone hydrogen-atom transfer (HAT) catalysis to activate native C-H bonds for multicomponent dicarbofunctionalization of alkenes. The ability to forge new carbon-carbon bonds between reagents typically viewed as commodity solvents provides a new, more atom-economic outlook for organic synthesis. Through detailed experimental and computational investigation, the critical effect of hydrogen bonding on the reactivity of this transformation was uncovered.

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16 results found


Open accessJournal ArticleDOI: 10.1021/ACS.CHEMREV.1C00263
06 Aug 2021-Chemical Reviews
Abstract: Direct photocatalyzed hydrogen atom transfer (d-HAT) can be considered a method of choice for the elaboration of aliphatic C-H bonds. In this manifold, a photocatalyst (PCHAT) exploits the energy of a photon to trigger the homolytic cleavage of such bonds in organic compounds. Selective C-H bond elaboration may be achieved by a judicious choice of the hydrogen abstractor (key parameters are the electronic character and the molecular structure), as well as reaction additives. Different are the classes of PCsHAT available, including aromatic ketones, xanthene dyes (Eosin Y), polyoxometalates, uranyl salts, a metal-oxo porphyrin and a tris(amino)cyclopropenium radical dication. The processes (mainly C-C bond formation) are in most cases carried out under mild conditions with the help of visible light. The aim of this review is to offer a comprehensive survey of the synthetic applications of photocatalyzed d-HAT.

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Topics: Molecule (53%), Bond cleavage (51%), Uranyl (51%) ... read more

6 Citations


Journal ArticleDOI: 10.1039/D1CS00399B
Shengqing Zhu1, Xian Zhao1, Huan Li1, Lingling Chu1Institutions (1)
Abstract: The catalytic dicarbofunctionalization of unsaturated π bonds represents a powerful platform for the rapid construction of complex motifs. Despite remarkable progress, novel and efficient methods for achieving such transformations under milder conditions with chemo-, regio-, and stereoselectivity still remain a significant challenge; thus, their development is highly desirable. Recently, the merging of nickel catalysis with radical chemistry offers a new and benign platform for the catalytic dicarbofunctionalization of unsaturated π bonds with unprecedented reactivity and selectivity. In this review, we summarize the recent advances in this area by underpinning the catalytic domino transformations involving radical capture by nickel to provide a clear overview of reaction designs and mechanistic scenarios.

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3 Citations


Journal ArticleDOI: 10.1021/JACS.1C05852
Guangyue Lei1, Meichen Xu1, Rui Chang1, Ignacio Funes-Ardoiz2  +1 moreInstitutions (2)
Abstract: Radical hydroalkylation of olefins enabled by hydrogen atom transfer (HAT) catalysis represents a straightforward means to access C(sp3)-rich molecules from abundant feedstock chemicals without the need for prefunctionalization. While Giese-type hydroalkylation of activated olefins initiated by HAT of hydridic carbon-hydrogen bonds is well-precedented, hydroalkylation of unactivated olefins in a similar fashion remains elusive, primarily owing to a lack of general methods to overcome the inherent polarity-mismatch in this scenario. Here, we report the use of visible-light-driven dual HAT catalysis to achieve this goal, where catalytic amounts of an amine-borane and an in situ generated thiol were utilized as the hydrogen atom abstractor and donor, respectively. The reaction is completely atom-economical and exhibits a broad scope. Experimental and computational studies support the proposed mechanism and suggest that hydrogen-bonding between the amine-borane and substrates is beneficial to improving the reaction efficiency.

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2 Citations


Journal ArticleDOI: 10.1039/D1CC02604F
Abstract: Visible-light-facilitated phosphorus radical reactions have been developed as a powerful and sustainable tool for the synthesis of various organophosphorus compounds. In general, these reactions require stoichiometric amounts of oxidants, and reductants, bases, and radical initiators, leading to uneconomical and complicated processes. Progress has been made over the past few years toward using reactions that proceed under eco-benign and mild reaction conditions. Furthermore, these reactions have broad functional group tolerance, with some facile and economical pathways. Herein, we summarize the discoveries and achievements pertaining to C–P bond formation through a visible light photocatalysis procedure with high atom economy, made by our group and other research groups. It was established that greener and more environmentally friendly approaches do not require an additional oxidant or base. Moreover, we have designed and synthesized a new type of P-radical precursor, which can take part in reactions without the requirement for any additional bases, oxidants, and additives. This breakthrough, pertaining to novel visible-light-induced transformations, will be discussed and a plausible mechanism is proposed, based on corresponding experiments and the literature.

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1 Citations


Open accessJournal ArticleDOI: 10.1002/CHEM.202103077
Abstract: The ruthenium-catalyzed synthesis of diarylmethane compounds was realized under exceedingly mild photoredox conditions without the use of exogenous photocatalysts. The versatility and robustness of the ruthenium-catalyzed C-H benzylation was reflected by an ample scope, including multifold C-H functionalizations, as well as transformable pyrazoles, imidates and sensitive nucleosides. Mechanistic studies were indicative of a photoactive cyclometalated ruthenium complex, which also enabled versatile C-H allylations.

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Topics: Ruthenium (51%)

1 Citations


References
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46 results found


Journal ArticleDOI: 10.1002/JCC.22885
Tian Lu1, Feiwu Chen1Institutions (1)
Abstract: Multiwfn is a multifunctional program for wavefunction analysis. Its main functions are: (1) Calculating and visualizing real space function, such as electrostatic potential and electron localization function at point, in a line, in a plane or in a spatial scope. (2) Population analysis. (3) Bond order analysis. (4) Orbital composition analysis. (5) Plot density-of-states and spectrum. (6) Topology analysis for electron density. Some other useful utilities involved in quantum chemistry studies are also provided. The built-in graph module enables the results of wavefunction analysis to be plotted directly or exported to high-quality graphic file. The program interface is very user-friendly and suitable for both research and teaching purpose. The code of Multiwfn is substantially optimized and parallelized. Its efficiency is demonstrated to be significantly higher than related programs with the same functions. Five practical examples involving a wide variety of systems and analysis methods are given to illustrate the usefulness of Multiwfn. The program is free of charge and open-source. Its precompiled file and source codes are available from http://multiwfn.codeplex.com.

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Topics: Population (52%), Plot (graphics) (51%)

9,777 Citations



Journal ArticleDOI: 10.1021/AR00113A004
05 Nov 1985-ChemInform
Topics: Captodative effect (69%)

512 Citations


Open accessJournal ArticleDOI: 10.1126/SCIENCE.AAF6123
Tian Qin1, Josep Cornella1, Chao Li1, Lara R. Malins1  +5 moreInstitutions (2)
13 May 2016-Science
Abstract: Alkyl carboxylic acids are ubiquitous in all facets of chemical science, from natural products to polymers, and represent an ideal starting material with which to forge new connections. This study demonstrates how the same activating principles used for decades to make simple C–N (amide) bonds from carboxylic acids with loss of water can be used to make C–C bonds through coupling with dialkylzinc reagents and loss of carbon dioxide. This disconnection strategy benefits from the use of a simple, inexpensive nickel catalyst and exhibits a remarkably broad scope across a range of substrates (>70 examples).

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Topics: Alkyl (57%), Amide (51%)

395 Citations


Open accessJournal ArticleDOI: 10.1021/ACS.JOC.5B02818
Huw M. L. Davies1, Daniel Morton1Institutions (1)

358 Citations


Performance
Metrics
No. of citations received by the Paper in previous years
YearCitations
20221
202115