Tamio Hayashi

Title: Recent Advances in Rhodium-Catalyzed Asymmetric Arylation

Prof.
Department of Chemistry, National Taiwan Normal University, Taipei 11677, Taiwan

EDUCATION

04/1972–03/1975            Ph D., Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Japan (Professor M. Kumada)

04/1970–03/1972            Master of Engineering, Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Japan

04/1966–03/1970            Bachelor of Engineering, Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Japan

PROFESSIONAL EXPERIENCES

02/2023–present          Professor (Yushan Scholar), Department of Chemistry, National Taiwan Normal University, Taiwan

02/2020–01/2023        Professor (Yushan Scholar), Department of Chemistry, National Tsing Hua University, Taiwan

05/2016–05/2019            Professor, Division of Chemistry and Biological Chemistry, School of Physical and                                                                  Mathematical Sciences, Nanyang Technological University, Singapore

01/2013–05/2016            Professor, Department of Chemistry, National University of Singapore, Singapore

04/2012–05/2016            Principal Scientist II, Institute of Materials Research and Engineering, A*STAR, Singapore

09/1994–03/2012            Professor, Department of Chemistry, Graduate School of Science, Kyoto University, Japan

04/1989–09/1994            Professor, Catalysis Research Center, Hokkaido University, Japan

04/1975–03/1989         Assistant Professor, Department of Synthetic Chemistry, Faculty of Engineering, Kyoto University, Japan

05/2011–03/2014         Visiting Professor, King Abdul-Aziz University, Jeddah, Saudi Arabia

09/2010–05/2016         Visiting Professor, Hong Kong Baptist University, Hong Kong

09/2002–08/2009         Chair Professor of Chirotechnology, Hong Kong Polytechnic University, Hong Kong

09/1976–08/1977            Postdoctoral Fellow, Colorado State University, USA (Professor L. S. Hegedus)

AWARDS/HONOURS

• The Order of the Sacred Treasure, Gold Rays with Neck Ribbon 2021(Emperor of Japan)

• Yamada–Koga Prize 2016 (Japan Research Foundation for Optically Active Compounds)

• Foundation Lectureship Award 2013 in Organic Chemistry, 2013 (Federation of Asian Chemical Societies)

• The Medal with Purple Ribbon (Shiju Hosho) 2010 (The Japanese Government)

• Khwarizmi International Award, 2010 (IROST, Iran)

• Author C. Cope Scholar Awards, 2008 (The American Chemical Society, USA)

• The Ryoji Noyori Prize, 2007 (The Society of Synthetic Organic Chemistry, Japan)

• Molecular Chirality Award, 2005 (Japan)

• Thomson Scientific Research Front Award, 2004 (Japan)

• The Chemical Society of Japan Award, 2003 (The Chemical Society of Japan)

• IBM Japan Science Prize, 1991 (Japan)

• The Society of Synthetic Organic Chemistry, Japan, Award for Young Scientists, 1983 (Japan)

• Negishi–Brown Lectures, 2014 (Purdue University, USA)

• Robert Robinson Lectureship, 2014 (Oxford University, UK)

• Boehringer-Ingelheim Lectureship, 2013 (Boston College, USA)

• Aldrich Lecturer, 2012 (The Scripps Research Institute)

• The Pfizer Lectureship, 2011 (Guelph-Waterloo Centre for Graduate Work in Chemistry and Biochemistry, Canada)

• AstraZeneca Lecture in Memory of Nils Löfgren, 2011 (Stockholm University, Sweden)

• The Pfizer & Sigma Aldrich Lecture, 2008 (University of Bristol, UK)

• Herbert C. Brown Lecturers, 2007 (Purdue University, USA)

• Boehringer Ingelheim Lecturer, 2007 (Université de Montréal, Canada)

• 2007 UC Irvine-Pfizer Symposium on Organic Synthesis, 2007 (University of California, Irvine, USA)

• Morris S. Kharasch Visiting Professor, 2006 (The University of Chicago, USA)

• The 20th Annual W. S. Johnson Symposium in Organic Chemistry, 2005 (Stanford University, USA)

• 2004 Pfizer Symposium, 2004 (Harvard University, USA)

• Oppolzer Lectures 2003, 2003 (Université de Genève, Switzerland)

• The Second Annual Merck/Caltech Symposium on Organic Synthesis, 2003 (Caltech, USA)

• Novartis Chemistry Lectureship 2001/2002 (Novartis, Switzerland)

• 2000-2001 Novartis Lecturer in Organic Chemistry, 2001 (Massachusetts Institute of Technology, USA)

EDITORIAL BOARD MEMBER

Tetrahedron Asymmetry: 1990–2017. Editor & Executive Board Member

Bull. Chem. Soc. Jpn.: 2012–present. Advisory Board

RESEARCH INTERESTS

• Organic Chemistry: Selective Organic Synthesis Catalyzed by Transition Metal Complexes, Asymmetric Catalysis

• Organometallic Chemistry: Mechanism of Catalytic Reactions

PUBLICATIONS

Selected Original papers in 2015-2024 (out of 611 publications, 55,050 total citations, H index = 132, Research.com) https://research.com/scientists-rankings/chemistry

1.    Desymmetrization of 2-(1,5-Dialkoxypent-3-yl)phenyl Grignard Reagents by Rhodium-Catalyzed Asymmetric 1,4-Shift/β-Alkoxy Elimination. Tsai, Y.-H.; Chen, Y.-H.; Sun, T.-W.; Chen, S.-W.; Wu, H.-L.; Hayashi, T. ACS Catalysis 2024, 14, 9505–9510. DOI: org/10.1021/acscatal.4c02879

2.    Ligand-Controlled Regiodivergent Arylation of Aryl(alkyl)alkynes and Asymmetric Synthesis of Axially Chiral 9-Alkylidene-9,10-dihydroanthracenes. Sun, C.; Qi, T.; Rahman, F.-U.; Hayashi, T.; Ming, J. Nature Commun. 2024, 15, 9307. DOI: org/10.1038/s41467-024-53767-4

3.    Carbon-Silicon-Switch Effect in Enantioselective Construction of Silicon-Stereogenic Center from Silacyclohexadienones. Yan, Y.; Wei, Q.; Su, Z.; Hang, N.-N.; Hayashi, T.; Ming, J.  Nature Commun. 2024, 15, 9915. DOI: org/10.1038/s41467-024-54241-x

4.    Secondary Phosphine Sulfide-Enabled Iridium-Catalyzed Asymmetric Allylic Substitution. Wu, Z.-H.; Wang, H.-Y.; Yang, H.-L.; Wei, L.-H.; Hayashi, H.; Duan W.-L. Angew. Chem. Int. Ed. 2022, 61, DOI: org/10.1002/anie.202213904

5.    Chiral Diene Ligands in Asymmetric Catalysis. Huang, Y.; Hayashi, T. Chem. Rev. 2022, 122, 14346–14404.

6.    Asymmetric Synthesis of Fluorinated Allenes by Rhodium-Catalyzed Enantioselective Alkylation/Defluorination of Propargyl Difluorides with Alkylzincs. Ng. J. S.; Hayashi, T. Angew. Chem. Int. Ed. 2021, 60, 20771–20775.

7.    Asymmetric Synthesis of Alkylzincs by Rhodium-Catalyzed Enantioselective Arylative Cyclization of 1,6-Enynes with Arylzincs. Chen, J.; Hayashi, T. Angew. Chem. Int. Ed. 2020, 59, 18510–18514.

8.    Synthesis of Arylacetaldehydes by Iridium-Catalyzed Arylation of Vinylene Carbonate with Arylboronic Acids. Wang, Z.; Xue, F.; Hayashi, T. Angew. Chem. Int. Ed. 2019, 58, 11054–11057.

9.    Enantioselective Synthesis of 3,3’-Diaryl-SPINOLS by Rh-Catalyzed Asymmetric Arylation–BF3-Promoted Spirocyclization Reactions. Yin, L.; Xing, J.; Wang, Y.; Shen, Y.; Lu, T.; Hayashi, T. Dou, X. Angew. Chem. Int. Ed. 2019, 58, 2474–2478.

10.   Addition of arylstannanes to alkynes giving ortho-alkenylarylstannanes catalysed cooperatively by a rhodium complex and zinc chloride. Ming, J.; Shi, Q.; Hayashi, T. Chem. Sci. 2018, 9, 7700–7704.

11.   Asymmetric Synthesis of Axially Chiral 2-Aminobiaryls by Rhodium-Catalyzed Benzannulation of 1-Arylalkynes with 2-(Cyanomethyl)phenylboronates. Xue, F.; Hayashi, T. Angew. Chem. Int. Ed. 2018, 57, 10368–10372.

12.   Rhodium-Catalyzed Enantioposition Selective Hydroarylation of Divinylphosphine Oxides with Arylboroxines. Wang, Z.; Hayashi, T. Angew. Chem. Int. Ed. 2018, 57, 1702–1706.

13.   Dynamic Kinetic Resolution in Rhodium-Catalyzed Asymmetric Arylation of Phospholene Oxides. Lim, K.M.-H.; Hayashi, T. J. Am. Chem. Soc. 2017, 139, 8122–8125.

14.   Rhodium-Catalyzed Asymmetric Arylation/Defluorination of 1-(Trifluoromethyl)alkenes Forming Enantioenriched 1,1-Difluoroalkenes. Huang, Y.; Hayashi, T. J. Am. Chem. Soc. 2016, 138, 12340–12343.

15.   Base Free Conditions for Rhodium-Catalyzed Asymmetric Arylation To Produce Stereochemically Labile α-Arylketones. Dou, X.; Lu, Y.; Hayashi, T. Angew. Chem. Int. Ed. 2016, 55, 6739–6743.

16.   Asymmetric Conjugate Alkynylation of Cyclic α,β-Unsaturated Carbonyl Compounds with a Chiral Diene–Rhodium Catalyst. Dou, X.; Huang, Y.; Hayashi, T. Angew. Chem. Int. Ed. 2016, 55, 1133–1137.

17.   Asymmetric Synthesis of Triarylmethanes by Rhodium-Catalyzed Enantioselective Arylation of Diarylmethylamines with Arylboroxines.  Huang, Y.; Hayashi, T. J. Am. Chem. Soc. 2015, 137, 7556–7559. 

18.   Rhodium-Catalyzed Asymmetric Arylation of Allyl Sulfones under the Conditions of Isomerization into Alkenyl Sulfones. Lim, K.M.-H.; Hayashi, T. J. Am. Chem. Soc. 2015, 137, 3201–3204. 

19.   Nickel-Catalyzed Three-Component Domino Reactions of Aryl Grignard Reagents, Alkynes, and Aryl Halides Producing Tetrasubstituted Alkenes. Xue, F.; Zhao, J.; Hor,T. S. A.; Hayashi, T. J. Am. Chem. Soc. 2015, 137, 3189–3192.  

20.   Tandem Catalysis of Amines Using Porous Graphene Oxide. Su, C.; Tandiana, R.; Balapanuru, J.; Tang, W.; Pareek, K.; Nai, C. T.; Hayashi, T.; Loh, K. P. J. Am. Chem. Soc. 2015, 137, 685–690.

Selected Papers with High Citation (citation numbers are those at 2024)

1.    Rhodium-Catalyzed Asymmetric 1,4-Addition and its Related Asymmetric Reactions. Hayashi, T; Yamasaki, K. Chem. Rev. 2003, 103, 2829–2844. [cited 1861]

2.    Catalytic Asymmetric Aldol Reaction: Reaction of Aldehydes with Isocyanoacetate Catalyzed by a Chiral Ferrocenylphosphine-Gold(I) Complex. Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405–6406. [cited 970]

3.    Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryl- and Alkenylboronic Acids to Enones. Takaya, Y.; Ogasawara, M.; Hayashi, T.; Sakai, M.; Miyaura, N. J. Am. Chem. Soc. 1998, 120, 5579–5580. [cited 862]

4.    Dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II): An Effective Catalyst for Cross-Coupling of Secondary and Primary Alkyl Grignard and Alkylzinc Reagents with Organic Halides. Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.; Hirotsu, K. J. Am. Chem. Soc. 1984, 106, 158–163. [cited 743]

5.    Catalytic Cycle of Rhodium-Catalyzed Asymmetric 1,4-Addition of Organoboronic Acids.  Arylrhodium, Oxa-π-allylrhodium, and Hydroxorhodium Intermediates. Hayashi, T.; Takahashi, M.; Takaya, Y.; Ogasawara. M. J. Am. Chem. Soc. 2002, 124, 5052–5058. [cited 734]

6.    Asymmetric Synthesis Catalyzed by Chiral Ferrocenylphosphine-Transition Metal Complexes.  I.  Preparation of Chiral Ferrocenylphosphines. Hayashi, T.; Mise, T.; Fukushima, M.; Kagotani, M.; Nagashima, N.; Hamada, Y.; Matsumoto, A.; Kawakami, S.; Konishi, M.; Yamamoto, K.; Kumada, M. Bull. Chem. Soc. Jpn. 1980, 53, 1138–1151. [cited 607] 

7.    A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts:  Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition. Hayashi, T.; Ueyama, K.; Tokunaga, N.; Yoshida, K. J. Am. Chem. Soc. 2003, 125, 11508–11509. [cited 579]

8.    Chiral Monodentate Phosphine Ligand MOP for Transition-Metal-Catalyzed Asymmetric Reactions. Hayashi, T. Acc. Chem. Res. 2000, 33, 354-362. [cited 589]

9.    C2-Symmetric Bicyclo[2.2.2]octadienes as Chiral Ligands: Their High Performance in Rhodium-Catalyzed Asymmetric Arylation of N-Tosylarylimines. Tokunaga, N.; Otomaru, Y.; Okamoto, K.; Ueyama, K.; Shintani, R.; Hayashi, T. J. Am. Chem. Soc. 2004, 126, 13584–13585. [cited 533]

10.   tert-Butoxide-Mediated Arylation of Benzene with Aryl Halides in the Presence of a Catalytic 1,10-Phenanthroline Derivative. Shirakawa, E.; Itoh, K.; Higashino, T.; Hayashi, T. J. Am. Chem. Soc. 2010, 132, 15537-15539. [cited 485]

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