Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Sun, Shang‐Zheng; Duan, Yaya; Mega, Riccardo S.; Somerville, Rosie J.; Martı́n, Rubén

doi:10.1002/ange.201916279

Cited by 30 publications

(8 citation statements)

References 81 publications

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“…[ 92 ] At the same time, Martin and coworkers also developed a photoredox/nickel‐catalyzed reductive alkylarylation of vinyl boronic esters using tertiary alkyl bromides and aryl bromides (Scheme 35). [ 93 ] These methods avoided preparation of pre‐activated substrates or organometallic reagents, thus simplifying the synthetic routes.…”

Section: Intermolecular Dicarbofunctionalization Of Alkenesmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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As a straightforward strategy for rapidly increasing molecular complexity, dicarbofunctionalization of alkenes has attracted substantial interests of organic synthesis, medicine chemistry, and materials science. Nickel-catalyzed cascade dicarbofunctionalizations have been flourished in this area recently, and nickel-mediated radical pathways particularly offer new opportunities in conjunctive cross-couplings with alkyl coupling partners. Herein, we give a comprehensive review of nickel-catalyzed dicarbofunctionalization of alkenes through a historical perspective, including intermolecular three-component reactions and intramolecular cascade reactions. Among the pathways discussed in this review, the carbometallation/cross-coupling process and the radical addition/cross-coupling process are the two major pathways for the nickel-catalyzed dicarbofunctionalization of alkenes. The oxidative cyclization and 1,2-metallate shift processes are also selectively discussed. These methods overcome the limitations associated with the reactions using noble metals in the field, providing an efficient and straightforward access to structurally diversified molecules. Yun-Cheng Luo (right) received his BSc degree in 2016 and master degree in 2019 from University of Science and Technology of China. Then he joined Professor Xingang Zhang's group at Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences to pursue his doctorate in organic chemistry. His research interests are focused on the activation of inert C-H or C-X bonds of bulky chemicals and their applications in the synthesis of fluorine-containing compounds. Chang Xu (middle) obtained his BSc degree in basic pharmacy from China Pharmaceutical University (China) in 2015. With an interest in organic chemistry and medicinal chemistry, he then began his graduate studies at Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences under the supervision of Professor Xingang Zhang. His research interests are focused on the activation and transformations of fluoroalkylanes and their applications in medicinal chemistry. Xingang Zhang (left) obtained his BSc degree in 1998 from Sichuan University (China) and received the Ph.D. in 2003 at Shanghai Institute of Organic Chemistry (SIOC), Chinese Academy of Sciences. After his postdoctoral work at University of Illinois at Urbana Champaign (USA), he joined the faculty team of SIOC as a research associate professor in 2008, and became research professor in 2012. His current research interests are focused on organofluorine chemistry and chemical biology.

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Section: Intermolecular Dicarbofunctionalization Of Alkenesmentioning

confidence: 99%

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

2020

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“…Given the known application of a-amino acids in metallaphotoredox-catalyzed two-compound cross-couplings, [5a] and the previous reliance on tertiary alkyl radical precursors in conjunctive cross-couplings, [7,13] we were intrigued by the unexpected high selectivity for conjunctive cross-coupling in our system and so proceeded to investigate the effect of steric factors on the reaction outcome (Scheme 3). The use of the primary a-amino acid Boc-Gly-OH gave none of the desired product 20, instead forming only the two-component crosscoupled product 20'.…”

Section: Communicationsmentioning

confidence: 99%

“…The unexpectedly high selectivity for conjunctive cross-coupling over direct two-component coupling in reactions of secondary a-amino acids is distinct from many previously reported radical-mediated conjunctive cross-couplings, which rely heavily on the use of tertiary alkyl radical precursors. [7,13] This allowed the reaction to be applied to a wide range of a-amino acids, and the synthetic utility of the method was highlighted in concise syntheses of four sedum alkaloids.…”

Section: Communicationsmentioning

confidence: 99%

“…Furthermore, incorporation of the versatile boronic ester into the product would provide a valuable functional handle for further manipulation. [12,13] Herein, we report the first example of a metallaphotoredoxcatalyzed decarboxylative conjunctive cross-coupling reaction between carboxylic acids, vinyl boronic esters, and aryl iodides. We focused on the use of secondary a-amino acids as substrates because 1) they are readily available and would provide access to structurally complex alkyl boronic ester products; and 2) we wished to address a limitation of previously reported metallaphotoredox-catalyzed conjunctive cross-couplings, which are mainly limited to reactions of tertiary alkyl radicals, [7] unless highly electrophilic conjunctive reagents are employed.…”

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Decarboxylative Conjunctive Cross‐coupling of Vinyl Boronic Esters using Metallaphotoredox Catalysis

et al. 2020

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The synthesis of complex alkyl boronic esters through conjunctive cross‐coupling of vinyl boronic esters with carboxylic acids and aryl iodides is described. The reaction proceeds under mild metallaphotoredox conditions and involves an unprecedented decarboxylative radical addition/cross‐coupling cascade of vinyl boronic esters. Excellent functional‐group tolerance is displayed, and application of a range of carboxylic acids, including secondary α‐amino acids, and aryl iodides provides efficient access to highly functionalized alkyl boronic esters. The decarboxylative conjunctive cross‐coupling was also applied to the synthesis of sedum alkaloids.

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“…However, in these cases, the enantiomeric excess (ee) values of the products were generally not ideal (<87%). Although several racemic couplings under reductive conditions have been developed [32][33][34][35][36] , to the best of our knowledge, asymmetric reductive cross-coupling with the dual catalytic system constitutes a potentially powerful yet unreported route to construct chiral benzylic boronic esters. Herein, we report a Ni/ photoredox-catalyzed asymmetric coupling with broad substrate scopes and excellent enantioselectivities (basically above 90% ee) by using a simple, commercially available ligand (Fig.…”

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Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters

et al. 2021

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The flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under a dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds under mild conditions (visible light, ambient temperature, no strong base) to access the versatile benzylic boronic esters with good functional group tolerance and excellent enantioselectivities.

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Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Cited by 30 publications

References 81 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Decarboxylative Conjunctive Cross‐coupling of Vinyl Boronic Esters using Metallaphotoredox Catalysis

Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters

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Site‐Selective 1,2‐Dicarbofunctionalization of Vinyl Boronates through Dual Catalysis

Cited by 30 publications

References 81 publications

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes†

Decarboxylative Conjunctive Cross‐coupling of Vinyl Boronic Esters using Metallaphotoredox Catalysis

Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters

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Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†

Nickel‐CatalyzedDicarbofunctionalization of Alkenes^†