Asymmetric Synthesis of Indoline from Achiral Phthalimide Involving Crystallization-Induced Deracemization.

Asymmetric synthesis was performed by combining the photochemical reaction of an achiral substrate followed by crystallization-induced deracemization. The results indicated that a fused indoline produced by photochemical intramolecular d-hydrogen abstraction and cyclization of N-(5-chloro-2-methylphenyl)phthalimide crystallized as a racemic conglomerate. Since this substrate has an aminal skeleton, racemization involving a ring-opening and ring-closing equilibrium process occurred under suitable conditions. Efficient racemization was observed in acetone containing a catalytic base, 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). Crystallization-induced dynamic deracemization by Viedma ripening from racemic indoline was performed with an excellent enantioselectivity of 99% ee. Furthermore, one-pot asymmetric synthesis of the indoline was achieved by the photochemical reaction of achiral phthalimide followed by continuous attrition-enhanced deracemization converging to 99% ee of enantiomeric crystals. This is the first example of asymmetric expression and amplification by photochemical hydrogen abstraction and crystallization-induced dynamic deracemization.

[1]  T. Omatsu,et al.  Chirogenesis and Amplification of Molecular Chirality Using Optical Vortices. , 2021, Angewandte Chemie.

[2]  Y. Yoshida,et al.  Asymmetric Anisoin Synthesis Involving Benzoin Condensation Followed by Deracemization , 2021 .

[3]  B. Feringa,et al.  Chiral Amplification of Phosphoramidates of Amines and Amino Acids in Water , 2021, Angewandte Chemie.

[4]  Y. Yoshida,et al.  Attrition-Enhanced Deracemization and Absolute Asymmetric Synthesis of Flavanones from Prochiral Precursors , 2020 .

[5]  Y. Yoshida,et al.  Chiral Symmetry Breaking of Thiohydantoins by Attrition-Enhanced Deracemization , 2020 .

[6]  Masami Sakamoto,et al.  Absolute Asymmetric Synthesis Involving Chiral Symmetry Breaking in Diels-Alder Reaction , 2020, Symmetry.

[7]  Y. Yoshida,et al.  Absolute Asymmetric Synthesis of Aspartic Acid Derivative from Prochiral Maleic Acid and Pyridine under Achiral Conditions. , 2019, Chemistry, an Asian journal.

[8]  Quan Wu,et al.  Palladium-Catalyzed Dearomative Arylvinylation Reaction of Indoles with N-Arylsulfonylhydrazones , 2019, Organometallics.

[9]  C. Bannwarth,et al.  Catalytic deracemization of chiral allenes by sensitized excitation with visible light , 2018, Nature.

[10]  Y. Yoshida,et al.  Asymmetric Diels-Alder Reaction Involving Dynamic Enantioselective Crystallization. , 2018, The Journal of organic chemistry.

[11]  Y. Yoshida,et al.  Asymmetric Synthesis Involving Reversible Photodimerization of a Prochiral Flavonoid Followed by Crystallization , 2017 .

[12]  J. Zhou,et al.  Nickel-Catalyzed Asymmetric Reductive Heck Cyclization of Aryl Halides to Afford Indolines. , 2017, Angewandte Chemie.

[13]  Yi‐Xia Jia,et al.  Enantioselective Dearomative Difunctionalization of Indoles by Palladium-Catalyzed Heck/Sonogashira Sequence. , 2017, Angewandte Chemie.

[14]  Pinhong Chen,et al.  Enantioselective Palladium(II)-Catalyzed Intramolecular Aminoarylation of Alkenes by Dual N-H and Aryl C-H Bond Cleavage. , 2017, Angewandte Chemie.

[15]  Y. Yoshida,et al.  Asymmetric Synthesis by Using Natural Sunlight under Absolute Achiral Conditions. , 2017, Chemistry.

[16]  Y. Yoshida,et al.  Asymmetric Synthesis of an Amino Acid Derivative from Achiral Aroyl Acrylamide by Reversible Michael Addition and Preferential Crystallization. , 2016, Chemistry.

[17]  N. Basarić,et al.  Photodecarboxylation of Adamantane Amino Acids Activated by Phthalimide , 2016 .

[18]  F. Rutjes,et al.  Emergence of single-molecular chirality from achiral reactants , 2014, Nature Communications.

[19]  H. Masu,et al.  Asymmetric transformation by dynamic crystallization of achiral succinimides. , 2013, Chemical communications.

[20]  C. Bolm,et al.  Enantioenrichment by iterative retro-aldol/aldol reaction catalyzed by an achiral or racemic base. , 2010, Chemistry.

[21]  Theo Rasing,et al.  Complete chiral symmetry breaking of an amino acid derivative directed by circularly polarized light. , 2009, Nature chemistry.

[22]  M. Mauksch,et al.  Generation of highly enantioenriched crystalline products in reversible asymmetric reactions with racemic or achiral catalysts. , 2009, Angewandte Chemie.

[23]  A. Griesbeck,et al.  Photoinduced-electron-transfer chemistry: from studies on PET processes to applications in natural product synthesis. , 2007, Accounts of chemical research.

[24]  G. Ferry,et al.  New ligands at the melatonin binding site MT(3). , 2006, European journal of medicinal chemistry.

[25]  P. Renard,et al.  Synthesis and biological activity of 6H-isoindolo[2,1-a]indol-6-ones, analogues of batracylin, and related compounds. , 2006, European journal of medicinal chemistry.

[26]  K. Lewis,et al.  Synthesis of functionalized 2-aryl-5-nitro-1H-indoles and their activity as bacterial NorA efflux pump inhibitors. , 2006, Bioorganic & medicinal chemistry.

[27]  Kenso Soai,et al.  Enantioselective synthesis of near enantiopure compound by asymmetric autocatalysis triggered by asymmetric photolysis with circularly polarized light. , 2005, Journal of the American Chemical Society.

[28]  Light Hermann Rau.  DIrect Asymmetric Photochemistry with Circularly Polarized Light , 2004 .

[29]  U. Yoon,et al.  The photochemistry of polydonor-substituted phthalimides: Curtin-Hammett-type control of competing reactions of potentially interconverting zwitterionic biradical intermediates. , 2004, Journal of the American Chemical Society.

[30]  Kenso Soai,et al.  Asymmetric autocatalysis and amplification of enantiomeric excess of a chiral molecule , 1995, Nature.

[31]  J. Bada.  Origins of homochirality , 1995, Nature.

[32]  K. Peters,et al.  Photo Electron Transfer Induced Macrocyclization of N‐Phthaloyl‐ω‐aminocarboxylic Acids , 1995 .

[33]  H. Schnering,et al.  Photoelektronentransfer‐induzierte Makrocyclisierung von N‐Phthaloyl‐ω‐aminocarbonsäuren , 1995 .

[34]  Stephen F. Mason,et al.  Origins of biomolecular handedness , 1984, Nature.

[35]  W. Elias.  The natural origin of optically active compounds , 1972 .

[36]  M. Sakamoto.  Asymmetric Synthesis Involving Dynamic Enantioselective Crystallization , 2020 .

[37]  E. Havinga.  Spontaneous formation of optically active substances. , 1954, Biochimica et biophysica acta.