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for Chemistry, University of Groningen, Groningen, The Netherlands

Gonzalo de Gonzalo, Department of Organic Chemistry, University of Seville, Seville, Spain

      Arnald Grabulosa, Departament de Química Inorgànica i Orgànica, Facultat de Química, Universitat de Barcelona, Barcelona, Spain, and Institut de Nanociència i Nanotecnologia (IN₂UB), Universitat de Barcelona, Barcelona, Spain

      Syuzanna R. Harutyunyan, Stratingh Institute for Chemistry, University of Groningen, Groningen, The Netherlands

      Freya M. Harvey, School of Natural Sciences, Department Chemie and Catalysis Research Center (CRC), Technische Universität München, Garching, Germany

      Yujiro Hayashi, Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan

      Kazuaki Ishihara, Graduate School of Engineering, Nagoya University, Nagoya, Japan

      Haruro Ishitani,Green & Sustainable Chemistry Social Cooperation Laboratory, Graduate School of Science, The University of Tokyo, Tokyo, Japan

      Loránd Kiss, Institute of Organic Chemistry, Research Centre for Natural Sciences, Budapest, Hungary

      Shū Kobayashi, Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan and Green & Sustainable Chemistry Social Cooperation Laboratory, Graduate School of Science, The University of Tokyo, Tokyo, Japan

      Kazuaki Kudo, Institute of Industrial Science, The University of Tokyo, Tokyo, Japan

      Azusa Kondoh, Graduate School of Science, Tohoku University, Sendai, Japan

      Jie Li, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China

      Xiao‐Bing Lu, State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian, China

      Jiyuan Lyu, Institut de Chimie des Substances Naturelles, Université Paris Saclay, Gif‐sur‐Yvette, France

      Dengke Ma, ICIQ – Institute of Chemical Research of Catalonia, Tarragona, Spain

      Géraldine Masson, Institut de Chimie des Substances Naturelles, Université Paris Saclay, Gif‐sur‐Yvette, France

      Mercedes Medio‐Simón, Department of Organic Chemistry, Pharmacy Faculty, University of Valencia, Valencia, Spain

      Paolo Melchiorre, ICIQ – Institute of Chemical Research of Catalonia, Tarragona, Spain and ICREA – Institució Catalana de Recerca i Estudis Avançats, Barcelona, Spain

      Edward Miller, University of California, Berkeley, Berkeley, CA, USA

      Patrick J. Moon, University of California, Berkeley, Berkeley, CA, USA

      Attila M. Remete, Institute of Pharmaceutical Chemistry, University of Szeged, Szeged, Hungary and Interdisciplinary Excellence Centre, Institute of Pharmaceutical Chemistry, University of Szeged, Szeged, Hungary

Antoni Riera, Departament de Química Inorgànica i Orgànica, Facultat de Química, Universitat de Barcelona, Barcelona, Spain and Institute for Research in Biomedicine (IRB Barcelona), The Barcelona Institute of Science and Technology (BIST), Barcelona, Spain

      Yonggui Robin Chi, Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore and Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang, China

      Tomislav Rovis, Department of Chemistry, Columbia University, New York, NY, USA

      Yuki Saito,Department of Chemistry, School of Science, The University of Tokyo, Tokyo, Japan

      Daniel M. Sedgwick, Department of Organic Chemistry, Pharmacy Faculty, University of Valencia, Valencia, Spain

      Yangyang Shen, Department of Chemistry, Columbia University, New York, NY, USA

      Takanori Shibata, Department of Chemistry and Biochemistry, Faculty of Science and Engineering, Waseda University, Tokyo, Japan

      Brian M. Stoltz, California Institute of Technology, Pasadena, CA, USA

      Bin Tan, Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

      Ken Tanaka, Department of Chemical Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan

      Masahiro Terada, Graduate School of Science, Tohoku University, Sendai, Japan

      F. Dean Toste, University of California, Berkeley, Berkeley, CA, USA

      Muhammet Uyanik, Graduate School of Engineering, Nagoya University, Nagoya, Japan

      Xavier Verdaguer, Departament de Química Inorgànica i Orgànica, Facultat de Química, Universitat de Barcelona, Barcelona, Spain and Institute for Research in Biomedicine (IRB Barcelona), The Barcelona Institute of Science and Technology (BIST), Barcelona, Spain

      Anton Vidal‐Ferran, Departament de Química Inorgànica i Orgànica, Facultat de Química, Universitat de Barcelona, Barcelona, Spain and Catalan Institution for Research and Advanced Studies (ICREA), Barcelona, Spain and _{Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Barcelona, Spain}

      Hongling Wang, Laboratory Breeding Base of Green Pesticide and Agricultural Bioengineering, Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University, Guiyang, China

      Tomasz Wdowik, Institut für Organische und Biomolekulare Chemie, Georg‐August‐Universität Göttingen, Göttingen, Germany

      Thomas Hin‐Fung Wong, ICIQ – Institute of Chemical Research of Catalonia, Tarragona, Spain

      Shaohua Xiang, Department of Chemistry, Southern University of Science and Technology, Shenzhen, China

      Jia‐Lei Yan, Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore, Singapore

      Xiao Zhang, Department of Chemistry, Columbia University, New York, NY, USA

PART I ASYMMETRIC ORGANOCATALYSIS

1 ASYMMETRIC ENAMINE AND IMINIUM ION CATALYSIS

      Yujiro Hayashi

       Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Japan

1.1. INTRODUCTION

Enamines are key reactive species in many asymmetric organocatalytic reactions. The field of asymmetric catalytic reactions involving an enamine as a reactive intermediate dates back to the seminal work in the 1970s on proline‐mediated intramolecular aldol reaction of triketone reported by Hajos and Parrish at Hoffmann‐La Roche [1] and Eder, Sauer, and Wiechert at Schering AG [2] (Eq. 1.1). In 2000, List, Lerner, and Barbas reported a proline‐mediated intermolecular aldol reaction (Eq. 1.2) [3], in which enamine is a key intermediate. In the same year, MacMillan reported a Diels‐Alder reaction catalyzed by a chiral imidazolidinone via an

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