Base Metal Catalysts for Photochemical C–H Borylation That Utilize Metal–Metal Cooperativity

Mazzacano, Thomas J.; Mankad, Neal P.

doi:10.1021/ja408861p

Cited by 245 publications

(205 citation statements)

References 36 publications

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“…However, the propensity of first-row transition metals to effect one-electron redox reactions makes them less likely to undergo 2-electron transformations typical of their heavier analogues. In order to circumvent this problem, several elegant strategies have been developed, notably using cooperativity between the metal and the redox-active ligands [1][2][3][4][5].…”

Section: Introductionmentioning

confidence: 99%

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Fontaine

Courtemanche

Légaré

et al. 2017

Coordination Chemistry Reviews

101

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This is the peer reviewed version of the following article: [Design Principles in Frustrated Lewis KeywordsFrustrated Lewis pairs, Ambiphilic molecules, Boron, Aluminum, Carbon dioxide, Methanol, C-H activation. Highlights 1.Phosphine-aluminum frustrated Lewis pairs (FLPs) can activate CO2 but show significant stability issues. 2.The Lewis acidity and basicity need to be fine-tuned to the desired reactivity for efficient FLP catalysis.3. FLP catalysts need to generate strong hydrides to reduce catalytically carbon dioxide. 4.Transition metal catalysis can serve as an inspiration for the design of metal-free catalysts for many transformations, including the borylation of heteroarenes. Graphical abstract AbstractThis account describes our work on the use of ambiphilic molecules as catalysts for the reduction of carbon dioxide. Starting with the discovery that aluminum ambiphilic species (Me2PCH2AlMe2)2 (1) and Al(C6H4-PPh3)3 (5) could coordinate CO2 but showed significant instability, we found that phosphinoborane Ph2P-2-Bcat-C6H4 (7) was an exceptional catalyst for the hydroboration of CO2 to methoxyboranes, a molecule that can be readily hydrolyzed to methanol. A mechanistic investigation allowed us to outline the similarities between the catalytic activity of frustrated Lewis pairs (FLPs) and that of transition metal complexes. We were able to extrapolate four important guidelines, described in this account, to synthesize efficient metal-free catalysts. We demonstrate that using these concepts it was possible to rationally design FLP catalysts for the C-H borylation of heteroarenes.

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Section: Introductionmentioning

confidence: 99%

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Fontaine

Courtemanche

Légaré

et al. 2017

Coordination Chemistry Reviews

101

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show abstract

“…While discrete synthetic examples containing metal-metal interactions have existed for decades, recent applications of multimetallic complexes in organometallic catalysis [4][5][6][7][8][9][10][11] and small molecule activation [12][13][14][15] have renewed significant interest in the fundamental structure, bonding and reactivity of this class of molecules, as well as the design and implementation of new bridging bifunctional supporting ligands.…”

Section: Introductionmentioning

confidence: 99%

Homo- and heteroleptic group 4 2-(diphenylphosphino)pyrrolide complexes: Synthesis, coordination chemistry and solution state dynamics

et al. 2014

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“…The optimal catalyst, (IPr)CuFeCp(CO) 2 , exhibited efficient activity at 5 mol% loading under photochemical conditions, showed only minimal decrease in activity upon reuse, and was able to catalyze borylation of a variety of arene substrates (Scheme 16). [33] In this paper, an effective strategy was developed on metal-metal cooperativity between two different base metals. Thus, this heterobimetallic Cu-Fe complex could be used as an efficient, robust, and versatile catalyst for C-H borylation, a sophisticated catalytic transformation of established importance to organic synthesis that previously required the use of noble metals, such as Rh or Ir.…”

Section: H E C H E M I C a L R E C O R Dmentioning

confidence: 99%

“…Iron/copper cocatalytic photochemical C-H borylation reported by Mazzacano and Mankad. [33] Scheme 17. Proposed mechanism for catalytic C-H borylation consisting of: i) bimetallic oxidative addition; ii) C2H functionalization; and iii) bimetallic reductive elimination.…”

Section: Iron/copper Cocatalyzed Borylation Of Aryl Bromides With Pinmentioning

confidence: 99%

The Application of Copper/Iron Cocatalysis in Cross-Coupling Reactions

Mao

Yan

Rong

et al. 2016

The Chemical Record

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For conventional cross-couplings in organic chemistry, precious metal (such as Pd or Rh) complexes have been the preferable choices as catalysts. However, their high cost, toxicity, and potential contamination of products limit their massive applications on some occasions, particularly in the pharmaceutical industry, where close monitoring of the metal contamination of products is required. Therefore, the use of metals that are less expensive and less toxic than Pd or Rh can be greatly advantageous and earth abundant metal (such Fe or Cu) catalysts have shown promise for replacing the precious metals. Interestingly, a certain copper catalyst combined with an iron catalyst displays higher catalytic efficiency than itself in various coupling reactions. Notably, ligand-free conditions make such protocols more useful and practical in many cases. In this account, we summarize the recent progress made in this increasingly attractive topic by describing successful examples, including our own work in the literature, regarding effective copper/iron cocatalysis. In addition, a few examples involving a magnetic and readily recyclable CuFe2 O4 nanoparticle cocatalyst are also included.

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Base Metal Catalysts for Photochemical C–H Borylation That Utilize Metal–Metal Cooperativity

Cited by 245 publications

References 36 publications

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Design principles in frustrated Lewis pair catalysis for the functionalization of carbon dioxide and heterocycles

Homo- and heteroleptic group 4 2-(diphenylphosphino)pyrrolide complexes: Synthesis, coordination chemistry and solution state dynamics

The Application of Copper/Iron Cocatalysis in Cross-Coupling Reactions

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