Dual Catalysis Strategies in Photochemical Synthesis

Skubi, Kazimer L.; Blum, Travis R.; Yoon, Tehshik P.

doi:10.1021/acs.chemrev.6b00018

Cited by 2,241 publications

(869 citation statements)

References 360 publications

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“…Moreover, this has allowed the merger of radical chemistry with other catalytic modalities to open up powerful new frontiers in synthetic chemistry. [15][16][17] Although the past decade has witnessed significant advances in this research area, the vast majority of studies have been limited to the functionalization of stabilized radicals (i.e., benzylic, allylic, α-carbonyl, α-heteroatom, polyhalogenated, etc. ), and methods using unactivated (i.e., -hydrogen-containing) radical precursors remain relatively scarce.…”

Section: Introductionmentioning

confidence: 99%

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp³)‐Substrates

Roslin

Odell

2017

Eur J Org Chem

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Over the past decade, visible-light photocatalysis has emerged as one of the brightest and most dynamic fields in modern organic chemistry. By employing a transition-metal-or organic-dye-based photocatalyst in conjunction with a low-energy visible-light source, this synthetic manifold allows the facile generation of radical intermediates that can subsequently be directed through a wide range of transformations. Although

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Section: Introductionmentioning

confidence: 99%

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp³)‐Substrates

Roslin

Odell

2017

Eur J Org Chem

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“…Thanks to the consequential advantages of alkyl carboxylic acids over alkyl halides in availability, stability and toxicity, the method and its underlying strategy are expected to have widespread uses in amine synthesis. The unique activity of copper-based catalysts in this decarboxylative C-N coupling contrasts the reign of nickel catalysis in analogous C-C coupling via tandem photoredox and metal catalysis 30,38,39 , underscoring their important divergences.…”

Section: Resultsmentioning

confidence: 97%

“…IV reacts with an aniline to give complex I and completes the metal catalytic cycle. This type of relay between photoredox catalysis and nickel catalysis has been exploited for C-C coupling 30,38,39 , and electron-transfer via photoredox catalysis is reported to promote C(sp 2 )-N reductive elimination 40,41 . However, a similar strategy has not been demonstrated for C(sp 3 )-N coupling.…”

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confidence: 99%

Decarboxylative C(sp3)–N cross-coupling via synergetic photoredox and copper catalysis

et al. 2018

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A mines are one of the most important structural motifs in pharmaceuticals, agrochemicals and organic materials 1,2 . Alkylation and reductive amination reactions are still commonly used to prepare and modify amines, and new methods derived from reductive amination, such as the borrowing hydrogen 3 strategy, have been reported [4][5][6][7] . Nevertheless, the most significant development in amine synthesis has been transition-metal-catalysed C-N coupling of aryl electrophiles (halides and pseudo halides) with amine nucleophiles [8][9][10][11] (Fig. 1a). The C-N coupling of alkyl electrophiles, however, is largely under-developed (Fig. 1a). A perceived difficulty is β -hydrogen elimination from a metal alkyl intermediate originated from oxidative addition of the alkyl electrophile, which has posed considerable challenges in analogous C-C crosscoupling of alkyl electrophiles [12][13][14] . Moreover, the product-yielding C(sp 3 )-N reductive elimination step is rarely demonstrated 15 . A notable exception is the light-induced, copper-catalysed C-N coupling of alkyl halides recently developed [16][17][18] . Nevertheless, the scope of amine nucleophiles is limited to carbazoles 16,18 and amides 17,19 . Alternative, formal C-N coupling of alkyl electrophiles via the addition of alkyl radicals to nitroarenes has been reported 20,21 .The group of Baran has recently trailblazed the use of redox-active esters derived from alkyl carboxylic acids as superior surrogates of alkyl halides in decarboxylative C-C cross-coupling reactions [22][23][24] . Extension to a decarboxylative carbon-heteroatom, particularly C-B bond formation has also been reported 19,[25][26][27][28][29] . The key attributes of alkyl carboxylic acids 30,31 are their unparalleled availability, stability and non-toxic nature, which are in stark contrast with alkyl halides, ketones and aldehydes. While several precedents of decarboxylative imidation 32 and amination 19,33 are known, they are limited to a narrow scope of very special substrates or intramolecular reactions. A general metal-catalysed decarboxylative C-N coupling of redox-active esters with anilines will provide valuable methodology for the synthesis of alkylated anilines (Fig. 1b), which requires alkyl halides and carbonyl compounds 6 as starting reagents using the currently standard methods of alkylation and reductive amination, respectively. Further foreseen advantages of such a decarboxylative amination include applicability to bulky primary and secondary alkyl groups and immunity to over-alkylation, both of which are major limitations of direct alkylation (Fig. 1b). Despite its conceptual simplicity and resemblance to decarboxylative C-C coupling, the intermolecular decarboxylative C-N coupling of redoxactive esters poses significant hurdles. The activation principle of redox-active esters originates from amide-bond synthesis; thus, amide formation can compete when amine nucleophiles are used. Moreover, decarboxylative C-C coupling reactions of redox-active esters were, until now, all init...

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“…Upon the irradiation of a solution composed of 1a, 2a,t he photocatalyst {Ir[dF(CF 3 )ppy] 2 (bpy)}PF 6 ,a nd Na 2 HPO 4 in MeOH followed by the additiono fa na queous HCl solution,t he mixture was heated at 80 8Ct ogive the desired tetrasubstituted furan 3a in 91 %y ield ( [10][11][12].…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Tetrasubstituted Furans by Using Photoredox‐Catalyzed Coupling of 2‐Bromo‐1,3‐dicarbonyl Compounds with Silyl Enol Ethers

et al. 2016

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Ap ractical and efficient method hasb een developed for the preparation of polysubstituted furans by using av isible-light-promoted photoredox approach. The one-pot synthesis involves ar adical cyclization/deprotection/aromatization reactions equence that proceeds smoothly under mild conditions, which makes this transformation ap owerful tool for the synthesis of av ariety of highly substitutedf urans.

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Dual Catalysis Strategies in Photochemical Synthesis

Cited by 2,241 publications

References 360 publications

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp³)‐Substrates

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp³)‐Substrates

Decarboxylative C(sp3)–N cross-coupling via synergetic photoredox and copper catalysis

Synthesis of Tetrasubstituted Furans by Using Photoredox‐Catalyzed Coupling of 2‐Bromo‐1,3‐dicarbonyl Compounds with Silyl Enol Ethers

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Dual Catalysis Strategies in Photochemical Synthesis

Cited by 2,241 publications

References 360 publications

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp3)‐Substrates

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp3)‐Substrates

Decarboxylative C(sp3)–N cross-coupling via synergetic photoredox and copper catalysis

Synthesis of Tetrasubstituted Furans by Using Photoredox‐Catalyzed Coupling of 2‐Bromo‐1,3‐dicarbonyl Compounds with Silyl Enol Ethers

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Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp³)‐Substrates

Visible‐Light Photocatalysis as an Enabling Tool for the Functionalization of Unactivated C(sp³)‐Substrates