Review
Chemistry, Multidisciplinary
Yan-Long Zheng, Stephen G. Newman
Summary: This article discusses two common families of chemical reactions - cross-coupling reactions and pi bond addition reactions - and the significant overlap between them. Recent advancements in catalysis have revealed the role of compounds such as esters, aldehydes, and alcohols in nickel- and palladium-catalyzed reactions, offering promising alternatives for the preparation of amides, ketones, substituted alcohols, alkanes, and more. The focus is on the key mechanistic steps that allow these non-traditional substrates to be incorporated into cross-coupling-like catalytic cycles.
CHEMICAL COMMUNICATIONS
(2021)
Article
Multidisciplinary Sciences
Wen-Tao Zhao, Wei Shu
Summary: We report a reaction mode for the enantioselective construction of alkyl-alkyl bond to access saturated stereogenic carbon centers by asymmetric reductive cross-coupling between different alkyl electrophiles in good yields with great levels of enantioselectivity. This reaction mode uses only alkyl electrophiles for enantioselective C-sp3-C-sp3 bond-formation, rendering reductive alkyl-alkyl cross-coupling as an alternative to traditional alkyl-alkyl cross-coupling reactions between alkyl nucleophiles and alkyl electrophiles to access saturated stereogenic carbon centers without the use of organometallic reagents. The reaction displays a broad scope for two alkyl electrophiles with good functional group tolerance. Mechanistic studies reveal that the reaction undergoes a single electron transfer that enabled the reductive coupling pathway to form the alkyl-alkyl bond.
Article
Chemistry, Multidisciplinary
Hua Huang, Qing-Song Dai, Hai-Jun Leng, Qing-Zhu Li, Si-Lin Yang, Ying-Mao Tao, Xiang Zhang, Ting Qi, Jun-Long Li
Summary: In this study, an NHC/photoredox dual catalytic cross-coupling of alkyl trifluoroborates with acid fluorides was developed. This method offers a novel solution for the classical acylative Suzuki coupling chemistry, allowing for the rapid synthesis of various ketones under mild conditions.
Article
Chemistry, Organic
Ling Zhao, Xiaochun He, Tianhua Cui, Xufeng Nie, Jiaqi Xu, Xueli Zheng, Weidong Jiang, Maolin Yuan, Hua Chen, Haiyan Fu, Ruixiang Li
Summary: The acceptorless dehydrogenative cross-coupling of primary alcohols to form cross-esters with the liberation of H2 gas was achieved using a [RuCl(eta 6-C6H6)(Kappa 2-CNP)][PF6]Cl complex as the catalyst. This sustainable protocol is applicable to a wide range of primary alcohols, particularly those that are sterically demanding, and it exhibits good functional group tolerance and high selectivity. The nitrogen-phosphine-functionalized N-heterocyclic carbene (CNP) ligand, which adopts a facial coordination mode and allows for facile dissociation of coordinated benzene, is responsible for the excellent catalytic performance.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Organic
Yukun Chen, Xiaoxiang Xi, Weiming Yuan
Summary: A photoinduced nickel-catalyzed reductive acyl-coupling reaction has been developed, enabling the synthesis of sterically bulky alpha-tertiary ketones. The reaction does not require an exogenous photocatalyst or a metal reductant, and various unstrained tertiary acyl electrophiles can be coupled with alkyl radicals under mild conditions, leading to the formation of all carbon quaternary aliphatic ketones, including alpha-tertiary amino ketones.
ORGANIC CHEMISTRY FRONTIERS
(2023)
Article
Chemistry, Organic
Zhi-Cheng Yu, You Zhou, Xiang-Long Chen, Jin-Tian Ma, Li-Sheng Wang, Yan-Dong Wu, An-Xin Wu
Summary: A reductive coupling reaction was established for the synthesis of diaryl 1,2-dicarbonyl compounds from aryl methyl ketones. The reaction involves C(CO)-C(sp3) bond cleavage and proceeds through an electron transfer process. Notably, this reaction is simple to operate, has mild reaction conditions, and is applicable to a wide range of substrates.
JOURNAL OF ORGANIC CHEMISTRY
(2022)
Article
Chemistry, Multidisciplinary
Jie Xu, Fangling Lu, Linghong Sun, Mingna Huang, Jianwei Jiang, Ke Wang, Dandan Ouyang, Lijun Lu, Aiwen Lei
Summary: The construction of C-S bonds plays a crucial role in synthetic, medicinal, and materials chemistry. In this study, we used an electrochemical reduction method to obtain thiyl radicals from sulfinic acids. This approach enabled the synthesis of a variety of desired thioesters in high yields. The preliminary mechanism studies revealed that the formation of thiyl radical species from sulfinic acid involved multiple steps of a single electron transfer process.
Article
Chemistry, Organic
Hang Yu, Zhong-Xia Wang
Summary: Alkyl aryl ketones were synthesized through a nickel-catalyzed reductive coupling reaction of arylcarboxylic acid (2-pyridyl)esters with alkyl methanesulfonates, both primary and secondary, under mild conditions. This methodology is compatible with various substrates and functional groups.
ORGANIC & BIOMOLECULAR CHEMISTRY
(2023)
Article
Chemistry, Organic
Eito Yoshioka, Hiroki Takahashi, Akane Kubo, Miki Ohno, Fuuka Watanabe, Rino Shiono, Yuuki Miyazaki, Hideto Miyabe
Summary: In this study, the cross dehydrogenative coupling reaction of aldehydes with methanol was investigated under organocatalytic conditions based on the cooperation between N-heterocyclic carbene and eosin Y·Na. The combined use of different catalysts and additives enabled the selective oxidation esterification of various aldehydes and simple cinnamaldehyde derivatives.
SYNTHESIS-STUTTGART
(2022)
Article
Multidisciplinary Sciences
Wen-Tao Zhao, Jian-Xin Zhang, Bi-Hong Chen, Wei Shu
Summary: This study reports an enantio-selective alkyl-alkyl cross-coupling reaction using a newly-developed chiral tridentate ligand. Two different alkyl halides were successfully cross-coupled to form α-tertiary aliphatic amides. The mechanism investigation revealed that one alkyl halide undergoes oxidative addition with nickel, while the other alkyl halide forms alkyl zinc reagents in situ, enabling reductive alkyl-alkyl cross-coupling without preformation of organometallic reagents.
NATURE COMMUNICATIONS
(2023)
Review
Chemistry, Multidisciplinary
Jianbin Li, Chia-Yu Huang, Chao-Jun Li
Summary: This review summarises recently developed strategies for achieving C-C cross-couplings between an inert aliphatic C-H bond and another C-H bond through different C(sp3)-H functionalisation tactics.
TRENDS IN CHEMISTRY
(2022)
Article
Chemistry, Organic
Kai Kang, Daniel J. Weix
Summary: This study successfully develops a two-step, one-pot protocol for the in situ generation of N-hydroxyphthalimide esters and their nickel-catalyzed cross-electrophile coupling with unactivated alkyl bromides, enabling the construction of C(sp3)-C(sp3) bonds. The conditions tolerate various functional groups, and mechanistic studies demonstrate the conversion of both substrates to alkyl radicals during the reaction.
Article
Chemistry, Multidisciplinary
Lingxiang Lu, Yi Wang, Wendy Zhang, Wen Zhang, Kimberly A. See, Song Lin
Summary: The cross-electrophile dialkylation of alkenes allows for regioselective dialkylation of alkenes without the use of transition-metal catalysts, leading to the formation of two C-(sp(3))-C-(sp(3)) bonds. This method provides a modular and efficient approach to building structural complexity in organic synthesis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Multidisciplinary
Jingyi Wang, Xuzhong Shen, Xu Chen, Yinwei Bao, Jian He, Zhan Lu
Summary: In this study, cobalt-catalyzed enantioconvergent cross-coupling of alpha-bromoketones with aryl zinc reagents was achieved, leading to the synthesis of chiral ketones with alpha-tertiary stereogenic centers. Ligand modification was found to be critical for improving the reactivity and selectivity of this transformation.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2023)
Article
Chemistry, Organic
Yingwei Wang, Mingrong Yang, Chichou Lao, Hanxuan Wang, Zhihong Jiang
Summary: An I-2-catalyzed oxidative cross-coupling reaction has been developed for the synthesis of α-carbonyl N,O-acetals with high functional group tolerance. The reaction allows the late-stage introduction of α-amino ketones into biorelevant alcohols and shows great generality for the functionalization of α-amino ketones.
JOURNAL OF ORGANIC CHEMISTRY
(2023)
Article
Chemistry, Organic
Geeta Devi Yadav, Pooja Chaudhary, Balaram Pani, Surendra Singh
Summary: Chiral transition metal complexes with privileged ligands are efficient catalysts for various asymmetric organic transformations. Transition metal complexes of C1-symmetric pyrrolidine-based ligands have been widely used in asymmetric organic reactions. However, a comprehensive review article on the transition metal complexes of chiral C1-symmetric pyrrolidine-based ligands derived from (L)-proline has not been published.
TETRAHEDRON LETTERS
(2024)
