Enantioselective Catalytic C-H Amidations: An Highlight Enantioselective Catalytic C-H Amidations: An Highlight

: The crucial role played by compounds bearing amide functions, not only in biological processes but also in several fields of chemistry, life polymers and material sciences, has brought about many significant discoveries and innovative approaches for their chemical synthesis. Indeed, a plethora of strategies has been developed to reach such moieties. Amides within chiral molecules are often associated with biological activity especially in life sciences and medicinal chemistry. In most of these cases, their synthesis requires extensive rethinking methodologies. In the very last years (2019–2020), enantioselective C-H functionalization has appeared as a straightforward alternative to reach chiral amides. Therein, an overview on these transformations within this timeframe is going to be given. Abstract: The crucial role played by compounds bearing amide functions, not only in biological processes but also in several fields of chemistry, life polymers and material sciences, has brought about many significant discoveries and innovative approaches for their chemical synthesis. Indeed, a plethora of strategies has been developed to reach such moieties. Amides within chiral molecules are often associated with biological activity especially in life sciences and medicinal chemistry. In most of these cases, their synthesis requires extensive rethinking methodologies. In the very last years (2019–2020), enantioselective C-H functionalization has appeared as a straightforward alternative to reach chiral amides. Therein, an overview on these transformations within this timeframe is going to be given.

[1]  E. Suresh,et al.  C-H Amidation and Amination of Arenes and Heteroarenes with Amide and Amine using Cu-MnO as a Reusable Catalyst under Mild Conditions. , 2021, The Journal of organic chemistry.

[2]  J. Ke,et al.  Transient- and Native-Directing-Group-Enabled Enantioselective C–H Functionalization , 2021, Synthesis.

[3]  F. Arnold,et al.  Navigating the Unnatural Reaction Space: Directed Evolution of Heme Proteins for Selective Carbene and Nitrene Transfer , 2021, Accounts of chemical research.

[4]  Xiaodong Yang,et al.  Room Temperature Benzofused Lactam Synthesis Enabled by Cobalt(III)‐Catalyzed C( sp 2 )−H Amidation , 2020, Advanced Synthesis & Catalysis.

[5]  L. Ackermann,et al.  Peptide Late-Stage Diversifications by Rhodium-Catalyzed Tryptophan C7 Amidation , 2020 .

[6]  Sukbok Chang,et al.  Highly Robust Iron Catalyst System for Intramolecular C(sp3)-H Amidation Leading to γ-Lactams. , 2020, Angewandte Chemie.

[7]  Ya-xi Yang,et al.  Rh(iii)-catalyzed tandem annulative redox-neutral arylation/amidation of aromatic tethered alkenes† , 2020, Chemical science.

[8]  Yafei Ji,et al.  Rhodium(III)-catalyzed C4-amidation of indole-oximes with dioxazolones via C-H activation. , 2020, Organic & biomolecular chemistry.

[9]  N. Mishra,et al.  Site‐Selective C–H Amidation of 2‐Aryl Quinazolinones Using Nitrene Surrogates , 2020 .

[10]  F. Michael,et al.  Catalytic Metal-free Allylic C-H Amination of Terpenoids. , 2020, Journal of the American Chemical Society.

[11]  N. Cramer,et al.  Catalytic Enantioselective Functionalizations of C-H Bonds by Chiral Iridium Complexes. , 2020, Chemical reviews.

[12]  Jingping Qu,et al.  Quinim: a New Ligand Scaffold Enabled Nickel-Catalyzed Enantioselective Synthesis of α-Alkylated γ-Lactam. , 2020, Journal of the American Chemical Society.

[13]  Alexander Fanourakis,et al.  Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate , 2020, ACS catalysis.

[14]  E. Meggers,et al.  Enantioselective Ring-Closing C–H Amination of Urea Derivatives , 2020, Chem.

[15]  M. Baik,et al.  Designing a Planar Chiral Rhodium Indenyl Catalyst for Regio- and Enantioselective Allylic C-H Amidation. , 2020, Journal of the American Chemical Society.

[16]  Rakesh Kumar,et al.  Co(III)-Catalyzed C-H Amidation of Nitrogen Containing Heterocycles with Dioxazolones under Mild Condition. , 2020, The Journal of organic chemistry.

[17]  J. Ke,et al.  Dual-Ligand-Enabled Ir(III)-Catalyzed Enantioselective C–H Amidation for the Synthesis of Chiral Sulfoxides , 2020 .

[18]  Bing‐Feng Shi,et al.  Achiral CpxIr(III)/Chiral Carboxylic Acid Catalyzed Enantioselective C–H Amidation of Ferrocenes under Mild Conditions , 2020, ACS Catalysis.

[19]  Minsoo Ju,et al.  Silver-Catalyzed Enantioselective Propargylic C-H Bond Amination Through Rational Ligand Design. , 2020, Journal of the American Chemical Society.

[20]  N. Chatani,et al.  The Direct Rh(III)-Catalyzed C-H Amidation of Aniline Derivatives Using a Pyrimidine Directing Group: The Selective Solvent Controlled Synthesis of 1,2-Diaminobenzenes and Benzimidazoles. , 2020, Organic letters.

[21]  N. Mishra,et al.  Phthalazinone-Assisted C-H Amidation Using Dioxazolones Under Rh(III) Catalysis. , 2020, The Journal of organic chemistry.

[22]  B. de Bruin,et al.  Dioxazolones: Stable Substrates for the Catalytic Transfer of Acyl Nitrenes , 2020, ACS Catalysis.

[23]  T. Uchida,et al.  Nitrene Transfer Reactions for Asymmetric C-H Amination: Recent Development , 2020 .

[24]  A. Hajra,et al.  Rhodium(iii)-catalyzed ortho-C-H amidation of 2-arylindazoles with a dioxazolone as an amidating reagent. , 2020, Organic & biomolecular chemistry.

[25]  S. Matsunaga,et al.  Diverse Approaches for Enantioselective C-H Functionalization Reactions Using Group 9 CpxMIII Catalysts. , 2020, Chemistry.

[26]  Ji‐Bao Xia,et al.  Transition-Metal-Catalyzed Intermolecular C–H Carbonylation toward Amides , 2020, Synlett.

[27]  L. Ye,et al.  Enantioselective Copper(I)/Chiral Phosphoric Acid Catalyzed Intramolecular Amination of Allylic and Benzylic C−H Bonds , 2019, Angewandte Chemie.

[28]  K. Houk,et al.  Non-C2-Symmetric Chiral-at-Ruthenium Catalyst for Highly Efficient Enantioselective Intramolecular C(sp3)-H Amidation. , 2019, Journal of the American Chemical Society.

[29]  Scott J. Miller,et al.  Co(III)-Catalyzed C-H Amidation of Dehydroalanine for the Site-Selective Structural Diversification of Thiostrepton. , 2019, Angewandte Chemie.

[30]  M. Kojima,et al.  Catalytic Enantioselective Methylene C(sp 3 )−H Amidation of 8‐Alkylquinolines Using a Cp*Rh III /Chiral Carboxylic Acid System , 2019, Angewandte Chemie.

[31]  Hujun Xie,et al.  Chameleon-like Behavior of the Directing Group in the Rh(III)-Catalyzed Regioselective C–H Amidation of Indole: An Experimental and Computational Study , 2019, ACS Catalysis.

[32]  Jie Huang,et al.  Cobalt-Catalyzed Ortho-C(sp2)-H Amidation of Benzaldehydes with Dioxazolones Using Transient Directing Groups. , 2019, Organic letters.

[33]  N. Cramer,et al.  Generation of Heteroatom Stereocenters by Enantioselective C–H Functionalization , 2019, ACS Catalysis.

[34]  S. Matsunaga,et al.  Chiral 2-Aryl Ferrocene Carboxylic Acids for the Catalytic Asymmetric C(sp3)–H Activation of Thioamides , 2019, Organometallics.

[35]  Xueli Wu,et al.  Intermolecular C-H Amidation of (Hetero)arenes to Produce Amides through Rhodium-Catalyzed Carbonylation of Nitrene Intermediates. , 2019, Angewandte Chemie.

[36]  F. Glorius,et al.  Intermolecular, Branch-Selective, and Redox-Neutral Cp*IrIII -Catalyzed Allylic C-H Amidation. , 2019, Angewandte Chemie.

[37]  J. Bacsa,et al.  Rh(III) and Ir(III)Cp* Complexes Provide Complementary Regioselectivity Profiles in Intermolecular Allylic C–H Amidation Reactions , 2019, ACS Catalysis.

[38]  Hao Wang,et al.  Iridium-Catalyzed Enantioselective C(sp3)-H Amidation Controlled by Attractive Noncovalent Interactions. , 2019, Journal of the American Chemical Society.

[39]  Matthew Burns,et al.  Asymmetric δ-Lactam Synthesis with a Monomeric Streptavidin Artificial Metalloenzyme. , 2019, Journal of the American Chemical Society.

[40]  Qi‐Jun Yao,et al.  Cp*Co(III)/MPAA-Catalyzed Enantioselective Amidation of Ferrocenes Directed by Thioamides under Mild Conditions. , 2019, Organic letters.

[41]  L. Ye,et al.  Chiral γ-lactam synthesis via asymmetric C–H amidation , 2019, Nature Catalysis.

[42]  Sukbok Chang,et al.  Asymmetric formation of γ-lactams via C–H amidation enabled by chiral hydrogen-bond-donor catalysts , 2019, Nature Catalysis.

[43]  Wing-Yiu Yu,et al.  Ruthenium(II)-Catalyzed Enantioselective γ-Lactams Formation by Intramolecular C-H Amidation of 1,4,2-Dioxazol-5-ones. , 2019, Journal of the American Chemical Society.

[44]  T. Rovis,et al.  Ir-Catalyzed Intermolecular Branch-Selective Allylic C-H Amidation of Unactivated Terminal Olefins. , 2019, Journal of the American Chemical Society.

[45]  S. Matsunaga,et al.  Enantioselective C(sp3 )-H Amidation of Thioamides Catalyzed by a CobaltIII /Chiral Carboxylic Acid Hybrid System. , 2019, Angewandte Chemie.

[46]  N. Cramer,et al.  Enantioselective Synthesis of Chiral‐at‐Sulfur 1,2‐Benzothiazines by CpxRhIII‐Catalyzed C−H Functionalization of Sulfoximines , 2018, Angewandte Chemie.

[47]  S. Buchwald,et al.  CuH-Catalyzed Asymmetric Hydroamidation of Vinylarenes. , 2018, Angewandte Chemie.

[48]  M. Baik,et al.  Selective formation of γ-lactams via C–H amidation enabled by tailored iridium catalysts , 2018, Science.

[49]  Preeti Rajput,et al.  Synthesis and biological importance of amide analogues , 2018 .

[50]  D. Dixon,et al.  Thioamide-Directed Cobalt(III)-Catalyzed Selective Amidation of C(sp3 )-H Bonds. , 2017, Angewandte Chemie.

[51]  N. Cramer,et al.  Cooperative Effects between Chiral Cpx -Iridium(III) Catalysts and Chiral Carboxylic Acids in Enantioselective C-H Amidations of Phosphine Oxides. , 2017, Angewandte Chemie.

[52]  D. Gamba‐Sánchez,et al.  Recent Developments in Amide Synthesis Using Nonactivated Starting Materials. , 2016, The Journal of organic chemistry.

[53]  J. Campagne,et al.  Nonclassical Routes for Amide Bond Formation. , 2016, Chemical reviews.

[54]  Sukbok Chang,et al.  Comparative Catalytic Activity of Group 9 [Cp*MIII] Complexes: Cobalt‐Catalyzed C—H Amidation of Arenes with Dioxazolones as Amidating Reagents. , 2016 .

[55]  L. Ackermann,et al.  Manganese(I)-Catalyzed C-H Aminocarbonylation of Heteroarenes. , 2015, Angewandte Chemie.

[56]  Sukbok Chang,et al.  Study of Sustainability and Scalability in the Cp*Rh(III)-Catalyzed Direct C–H Amidation with 1,4,2-Dioxazol-5-ones , 2015 .

[57]  Sukbok Chang,et al.  Mechanistic studies on the Rh(III)-mediated amido transfer process leading to robust C-H amination with a new type of amidating reagent. , 2015, Journal of the American Chemical Society.

[58]  T. Uchida,et al.  Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-H amination using azide compounds as nitrene precursors. , 2014, Chemical record.

[59]  Sukbok Chang,et al.  Mechanistic studies of the rhodium-catalyzed direct C-H amination reaction using azides as the nitrogen source. , 2014, Journal of the American Chemical Society.

[60]  Allan M Jordan,et al.  The medicinal chemist's toolbox: an analysis of reactions used in the pursuit of drug candidates. , 2011, Journal of medicinal chemistry.

[61]  T. Mei,et al.  Pd(II)-Catalyzed Amination of C—H Bonds Using Single-Electron or Two-Electron Oxidants. , 2010 .

[62]  J. S. Carey,et al.  Analysis of the reactions used for the preparation of drug candidate molecules. , 2006, Organic & biomolecular chemistry.

[63]  S. Buchwald,et al.  Combined C-H functionalization/C-N bond formation route to carbazoles. , 2005, Journal of the American Chemical Society.

[64]  C. Breneman,et al.  The amide linkage : structural significance in chemistry, biochemistry, and materials science , 2003 .