Organocatalytic Asymmetric Construction of Tetrasubstituted Carbon Stereocenters Bearing Three Heteroatoms via Intramolecular Cyclization of Vinylidene ortho-Quinone Methide with Imidates.

We report herein an organocatalytic asymmetric protocol for the construction of tetrasubstituted carbon stereocenters bearing three heteroatoms. The reaction proceeded via the enantioselective intramolecular cyclization reaction of vinylidene ortho-quinone methide (VQM) with imidates to form pentacyclic heterocycles. The formed tetrasubstituted carbon center was stable under a high temperature and the conditions for further transformations.

[1]  Hailong Yan,et al.  Atroposelective Construction of Nine-Membered Carbonate Bridged Biaryls. , 2022, Angewandte Chemie.

[2]  Haihong Huang,et al.  Mild, metal-free synthesis of 2-substituted quinazolinones from imidates and methyl 2-aminobenzoates or 2-aminobenzamides , 2022, Tetrahedron.

[3]  Hailong Yan,et al.  Organocatalytic Asymmetric Dearomatizing Hetero-Diels-Alder Reaction of Nonactivated Arenes. , 2022, Journal of the American Chemical Society.

[4]  Hailong Yan,et al.  An Isolable Vinylidene ortho-Quinone Methide: Synthesis, Structure and Reactivity. , 2022, Angewandte Chemie.

[5]  Hailong Yan,et al.  Diversity-oriented enantioselective construction of atropisomeric heterobiaryls and N-aryl indoles via vinylidene ortho-quinone methides (VQMs) , 2021 .

[6]  S. Ye,et al.  Dynamic Kinetic Resolution of α-Trifluoromethyl Hemiaminals without α-Hydrogen via NHC-Catalyzed O-Acylation. , 2021, Organic Letters.

[7]  B. Liu,et al.  Carbene-Catalyzed Enantioselective Aldol Reaction: Post-Aldol Stereochemistry Control and Formation of Quaternary Stereogenic Centers. , 2020, Angewandte Chemie.

[8]  T. Talele.  Opportunities for Tapping into Three-Dimensional Chemical Space Through a Quaternary Carbon. , 2020, Journal of medicinal chemistry.

[9]  Tianli Wang,et al.  Highly Enantioselective Construction of Fully Substituted Stereocenters Enabled by In Situ Phosphonium-Containing Organocatalysis , 2020 .

[10]  R. Nandi,et al.  Benzimidates as gem-Diamidation and Amidoindolyzation Cascade Synthons with a Hydrated NiII Catalyst. , 2020, Organic letters.

[11]  Jing-ru Zhang,et al.  Synthesis of 2,4‐Diaryl‐1,3‐benzoxazines via FeCl 3 ‐Catalyzed Annulation of ortho ‐Hydroxyphenyl‐Substituted para ‐Quinone Methides with Imidates , 2019, Advanced Synthesis & Catalysis.

[12]  Rong Zeng,et al.  Highly Chemo- and Diastereoselective Construction of Quaternary Stereocenters through Palladium-Catalyzed [3 + 2] Cyclization of 5-Alkenyl Thiazolones. , 2019, Organic letters.

[13]  G. He,et al.  Copper(I)-Catalyzed Enantioselective Intramolecular Aminotrifluoromethylation of O-Homoallyl Benzimidates. , 2019, Organic letters.

[14]  Z. Su,et al.  Bimetallic Catalytic Asymmetric Tandem Reaction of β-Alkynyl Ketones to Synthesize 6,6-Spiroketals. , 2019, Angewandte Chemie.

[15]  Hailong Yan,et al.  Organocatalytic Asymmetric One-Step Desymmetrizing Dearomatization Reaction of Indoles: Development and Bioactivity Evaluation. , 2018, Angewandte Chemie.

[16]  J. W. Ward,et al.  Asymmetric α-arylation of amino acids , 2018, Nature.

[17]  Jian Zhou,et al.  Development of Synthetic Methodologies via Catalytic Enantioselective Synthesis of 3,3-Disubstituted Oxindoles. , 2018, Accounts of chemical research.

[18]  Hailong Yan,et al.  Organocatalytic Intramolecular [4+2] Cycloaddition between In Situ Generated Vinylidene ortho-Quinone Methides and Benzofurans. , 2017, Angewandte Chemie.

[19]  T. Talele.  Natural-Products-Inspired Use of the gem-Dimethyl Group in Medicinal Chemistry. , 2017, Journal of medicinal chemistry.

[20]  David A. Nagib,et al.  Directed β C-H Amination of Alcohols via Radical Relay Chaperones. , 2017, Journal of the American Chemical Society.

[21]  L. Ackermann,et al.  Domino C–H/N–H Allylations of Imidates by Cobalt Catalysis , 2017 .

[22]  Jian Zhou,et al.  Catalytic Enantioselective Desymmetrization Reactions to All-Carbon Quaternary Stereocenters. , 2016, Chemical reviews.

[23]  M. Kanai,et al.  Rhenium-Catalyzed Synthesis of 1,3-Diiminoisoindolines via Insertion of Carbodiimides into a C-H Bond of Aromatic and Heteroaromatic Imidates. , 2016, Organic letters.

[24]  B. Stoltz,et al.  Catalytic enantioselective construction of quaternary stereocenters: assembly of key building blocks for the synthesis of biologically active molecules. , 2015, Accounts of chemical research.

[25]  L. Overman,et al.  Catalytic enantioselective synthesis of quaternary carbon stereocentres , 2014, Nature.

[26]  F. Glorius,et al.  Conjugate umpolung of β,β-disubstituted enals by dual catalysis with an N-heterocyclic carbene and a Brønsted acid: facile construction of contiguous quaternary stereocenters. , 2014, Angewandte Chemie.

[27]  F. Glorius,et al.  Rh(III)/Cu(II)-cocatalyzed synthesis of 1H-indazoles through C-H amidation and N-N bond formation. , 2013, Journal of the American Chemical Society.

[28]  Jian Zhou,et al.  Organocatalytic asymmetric synthesis of substituted 3-hydroxy-2-oxindoles via Morita-Baylis-Hillman reaction. , 2010, Journal of the American Chemical Society.

[29]  Jian Zhou,et al.  Catalytic Asymmetric Synthesis of Oxindoles Bearing a Tetrasubstituted Stereocenter at the C‐3 Position , 2010 .

[30]  Kazunobu Igawa,et al.  Vinylidene ortho-Quinone Methides: Unique Chiral Reaction Intermediates in Catalytic Asymmetric Synthesis. , 2018, Chimia.