Hisashi Yamamoto Professor
Born Kobe, Japan, 1943.
Kyoto University, B. S., 1967.
Harvard University, Ph. D., 1971.
Kyoto University, Assistant Professor, 1972- 1977.
The University of Hawaii, Associate Professor, 1977-1980.
Nagoya University, Associate Professor, 1980-1983.
Nagoya University, Professor, 1983-2002.
The University of Chicago, Professor, 2002-.
2009 Grand Prize of Synthetic Organic Chemistry of Japan
2009 ACS Award for Creative Work in Synthetic Organic Chemistry
2008 Honorary Fellow of the Chemical Research Society of India
2008 Honorary Member of the Chemical Society of Japan
2007 Humboldt Research Award
2007 Japan Academy Prize
2006 Tetrahedron Prize
2003 Molecular Chirality Award
2003 Fellow of AAAS
2002 National Prize of Purple Medal (Japan)
2002 Tetrahedron Chair
2002 Le Grand Prix de la Fondation Maison de la Chimie
1998 Max-Tishler Prize
1997 Toray Science and Technology Award
1995 The Chemical Society of Japan Award
1994 Merck-Schuchardt Lectureship
1993 Prelog Medal
1992 Chunichi Award
1991 Houkou Award
1988 IBM Science Award
1988 Organic Reaction Lecturer
1977 The Chemical Society of Japan Award for Young Chemist
OFFICE: GHJ 409 , 5735 S Ellis Ave, Chicago, IL 60637
Chemists' ability to perform syntheses on a routine basis is due in large part to the development of new methods for synthesizing organic molecules which would have been impossible just a few decades ago. The availability of such new methods of synthesis has increased not only the range of structures which can be assembled but also the ease and economy of synthesis. During the past 30 years of his research, Professor Hisashi Yamamoto has had a tremendous impact on the field of organic chemistry through his reports of dramatic new advances in organic synthesis. Yamamoto's publications are numerous (over 450), and almost every one of them has provided an innovative new development or idea. Applications of this original and versatile chemistry have allowed him and other scientists to realize truly efficient syntheses of organic molecules of both theoretical and practical importance.
Hisashi Yamamoto has uncovered novel aspects of Lewis and Brønsted acid catalysts in selective organic synthesis. During his career he has discovered a wide variety of powerful new synthetic reactions, reagents, and catalysts based on acid catalysis chemistry. Through his dedicated efforts, Lewis and Brønsted acid are now recognized as major tools in the synthesis of both simple and complex organic molecules. Among Yamamoto's many superb contributions the following are especially worthy of mention.
His research in the area of organoaluminum chemistry has had a great impact on synthetic organic chemistry. The strong Lewis acidity of organoaluminum compounds appears to account for their strong tendency to form a stable 1:1 complex. Thus, the coordination of molecules invariably causes a change of reactivity, and the coordinated group may be activated or deactivated depending upon the type of reaction. Furthermore, with coordination of organic molecules an auxiliary bond can become coupled to the reagent and promote the desired reaction. In short, the reagents make a combined Lewis acid - Lewis base attack on a substrate with less activation energy, a field opened by Yamamoto's early and highly original studies. His aluminum amide reagents for epoxide rearrangement, biogenetic-type terpene synthesis, and the Beckmann rearrangement-alkylation reaction sequence are notable examples.
He was intrigued by the chemistry of the carbonyl compound-Lewis acid complex and introduced the unusually bulky organoaluminum reagents, methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) and aluminum tris(2,6-diphenylphenoxide) (ATPH). These reagents were successfully utilized for the selective alkylation of cyclic ketones and aldehydes to generate equatorial alcohol and an anti-Cram type product, respectively, for trans- and cis-selective Claisen rearrangement, for regioselective Diels-Alder reaction, and for epoxide-aldehyde rearrangement. The ATPH - aromatic carbonyl complex reacts with nucleophiles selectively at the para-position of the aromatic ring to generate cyclohexadiene derivatives.
After these pioneering researches in Lewis acid chemistry, Yamamoto has become aware of the vast importance of chiral Lewis acids in modern asymmetric synthesis. In 1985, he first introduced binaphthol as a key ligand for chiral Lewis acid catalysts. This work was the forerunner of a vast quantity of present-day research on the binaththol based chiral Lewis acid catalyst. Based on his knowledge of organoaluminum chemistry, he designed a new and powerful organoaluminum catalyst for asymmetric hetero-Diels-Alder reaction. It was his Brønsted acid-Lewis acid combined system, however, which gave him a unique opportunity for the most efficient asymmetric Lewis acid catalyst for Diels-Alder reaction. A similar concept was employed for his catalytic asymmetric protonation under acidic conditions, which now creates a long sought proton induced asymmetric polyene cyclization.
His discovery of tartaric acid based catalyst (CAB catalyst) and amino acid based catalyst led to the first enantioselective Diels-Alder reaction of a broad range of dienes and dienophiles. The same catalyst was shown to be the first highly efficient catalyst for asymmetric aldol and ene type reactions. The reaction is simple, exceedingly stereoselective, and environmentally friendly.
Direct condensation of carboxylic acids by alcohols or amines is the most important transformation of organic synthesis. Yamamoto found Lewis acid catalyst could play an important role for such esterification and amidation processes. For example, his new hafnium catalyzed esterification and boron catalyzed amidation are now becoming increasingly important to the chemical industry.
More recently, he has developed new asymmetric oxidation processes based on an acid catalysis concept. His nitroso chemistry offers an entirely new access to selective organic synthesis and provides catalytic enantioselective reaction to introduce oxygen and/or nitrogen into the molecule. His pyridine based nitroso- and azo-hetero-Diels-Alder provides powerful tool for asymmetric synthesis. He also recently reported asymmetric epoxidation of homoallylic alcohols based on new vanadium catalyst, one of the most difficult asymmetric oxidations to date.
After moving to Chicago, he proposed the use of 8-hydroxyquinole based chiral Lewis acid catalysis. The catalyst is designed as a rigid metal complex of cis-b-configuation. The reagent turned out to be a brand-new "privileged ligand" for asymmetric synthesis. Catalytic asymmetric pinacol coupling, NH reaction, Mukaiyama-Michael addition, and Pudovik reactions are now able to proceed with complete enantioselectivities.
His laboratory is also noted for its introduction of metal reagents that allow highly selective SN2 cross coupling with carbonyl and allylic electrophiles. Allylic organobarium reagent, so-called "Yamamoto's reagent", reacts with a variety of electrophiles selectively at less substituted termini with complete stereospecificity, resolving a long-standing problem in terpene synthesis.
Each of the new methodologies developed by Yamamoto has been characterized by careful design of reagent/catalyst which provides a highly practical solution to a tough synthetic problem.
Selected References (Total >490 publications and >100 reviews)
1. Organoaluminum reagents of type R1R2NAIEt2 which allow regiospecific isomerization of epoxides to allylic alcohols. Yasuda, A.; Tanaka, S.; Oshima, K.; Yamamoto, H.; Nozaki, H., J. Am. Chem. Soc., 96, 6513 (1974).
2. Successive Beckmann rearrangement-alkylation sequence by organoaluminium reagents. A simple rout to dl-pumiliotoxin C., Hattori, K.; Matsumura, Y.; Miyazaki, T.; Maruoka, K.; Yamamoto, H., J. Am. Chem. Soc., 103, 7368 (1981).
3. Methylaluminum bis(2,6-di-tert-butyl-4-alkylphenoxide). A new reagent for obtaining unusual equatorial and anti-Cram selectivity in carbonyl alkylation. Maruoka, K.; Itoh, A.; Yamamoto, H., J. Am. Chem. Soc. 107, 4573 (1985).
4. Asymmetric cyclization of unsaturated aldehydes catalyzed by a chiral Lewis acid. Sakane, S.; Maruoka, K.; Yamamoto, H., Tetrahedron Lett, 26, 5535. (1985).
5. Asymmetric hetero-Diels-Alder reaction catalyzed by chiral organoaluminum reagent. Maruoka, K.; Itoh, T.; Shirasaka, T.; Yamamoto, H., J. Am. Chem. Soc., 110, 310 (1988).
6. Acyloxyborane: An activating device for carboxylic acids. Furuta, K.; Miwa, Y.; Iwanaga, K.; Yamamoto, H., J. Am. Chem. Soc., 110, 6254 (1988).
7. Organoaluminum-promoted Claisen rearrangement of allyl vinyl ethers. Nonoshita, K.; Banno, H.; Maruoka, K.; Yamamoto, H., J. Am. Chem. Soc., 112, 316 (1990).
8. Catalytic asymmetric aldol reactions. Use of a chiral acyloxyborane complex as a versatile Lewis Acid Catalyst. Furuta, K.; Maruyama, T.; Yamamoto, H. J. Am. Chem. Soc. 113, 1041 (1991).
9. Chiral (acyloxy)borane catalyzed asymmetric allylation of aldehydes. Furuta, K.; Mouri, M.; Yamamoto, H. Synlett 561 (1991).
10. Allylbarium in Orgainic Synthesis: Unprecedented a-selective and stereospecific allylation of carbonyl compounds. Yanagisawa, A.; Habaue, S.; Yamamoto, H., J. Am. Chem. Soc. 113, 8955 (1991).
11. Brønsted acid assisted chiral Lewis acid (BLA) catalyst for asymmetric Diels-Alder reaction. Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc., 116, 1561 (1994).
12. Lewis acid assisted chiral Brønsted acid for enantioselective protonation of silyl enol ethers and ketene bis(trialkylsily) acetals. Ishihara, K.; Kaneeda, M.; Yamamoto, H. J. Am. Chem. Soc., 116, 11179 (1994).
13. Catalytic asymmetric allyation of aldehydes using a chiral silver (I) complex. Yanagisawa, A.; Nakashima, H.; Ishiba, A.; Yamamoto, H. J. Am. Chem. Soc., 118, 4723 (1996).
14. Aluminum tris(2,6-diphenylphenoxide)-ArCOCI complex for nucleophilic dearomatic functionalization. Saito, S.; Sone, T.; Murase, M.; Yamamoto, H. J. Am. Chem. Soc., 122, 10216 (2000).
15. Direct condensation of carboxylic acids with alchols catalyzed by hafnium(IV) salts. Ishihara, K.; Ohara, S.; Yamamoto, H. Science, 290, 1140 (2000).
16. Lewis acid promoted, O-selective nucleophilic addition of silyl enol ethers to N=O bonds. Momiyama, N.; Yamamoto, H. Angew. Chem. Int. Ed. Enl., 41, 2986 (2002).
17. Enantioselective O- and N-Nitroso Aldol Synthesis of Tin Enolates. Isolation of Three BINAP-Silver Complexes and Their Role in Regio- and Enantioselectivity. Momiyama, N.; Yamamoto, H. J. Am. Chem. Soc., 126, 5360 (2004).
18. Catalytic, Highly Enantio, and Diastereoselective Nitroso Diels-Alder Reaction. Yamamoto, Y.; Yamamoto, H., J. Am. Chem. Soc., 126, 4128 (2004).
19. A New Artificial Cyclase for Polyprenoids: Enantioselective Total Synthesis of (-)-Chromazonarol, (+)-8- epi-Puupehedione, and (-)-11´-Deoxytaondiol Methyl Ether. Ishibashi, H., Ishihara, K.; Yamamoto, H. J. Am. Chem. Soc.126, 11122 (2004).
20. Catalytic, Highly Enantio- and Diastereoselective Pinacol Coupling Reaction with a New Tethered Bis(8-quinolinolato) Ligand. Takenaka, N.; Xia, G.; Yamamoto, H. J. Am. Chem. Soc.,126, 13198 (2004)
21. Brønsted Acid Catalysis of Achiral Enamine for Regio- and Enantioselective Nitroso Aldol Synthesis. Momiyama, N.; Yamamoto, H. J. Am. Chem. Soc.,127, 1080 (2005)
22. Silver-Catalyzed Asymmetric Sakurai-Hosomi Allylation of Ketones. Wadamoto, M.; Yamamoto, H. J. Am. Chem. Soc., 127, 14556-14557, (2005)
23. Tris(trimethylsilyl)silyl-Governed Aldehyde Cross-Aldol Cascade Reaction. Boxer, M. B.; Yamamoto, H. J. Am. Chem. Soc., 128, 48-49, (2006)
24. Catalytic Enantioselective Nozaki-Hiyama Allylation Reaction with Tethered Bis(8-quinolinolato) (TBOx) Chromium Complex. Xia, G.; Yamamoto, H. J. Am. Chem. Soc., 128, 2554-2555 (2006).
25. Vanadium-Catalyzed Asymmetric Epoxidation of Homoallylic Alcohols Zhang, W.; Yamamoto, H. J. Am. Chem. Soc. 129, 286 (2007).
26. Catalytic Enantioselective Allenylation Reactions of Aldehydes with Tethered Bis(8-quinolinolato) (TBOx) Chromium Complex Xia, Guoyao; Yamamoto, H., J. Am. Chem. Soc. 129, 496 (2007).
27. Asymmetric Conjugate Addition of Silyl Enol Ethers Catalyzed by Tethered Bis(8-quinolinolato)Aluminum Complexes Takenaka, N.; Abell, J.P.; Yamamoto, H. J. Am. Chem. Soc. 129, 742 (2007).
28. Diastereo- and Enantioselective Synthesis of Nitroso Diels- Alder-type Bicycloketones Using Dienamine: Mechanistic Insight into Sequential Nitroso Aldo/Michael Reaction and Application for Optically Pure 1-Amino-3,4-diol Synthesis J. Am. Chem. Soc. 129, 1190 (2007).
29. “Super Silyl” Group for Diastereoselective Sequential Reactions: Access to Complex Chiral Architecture in One Pot. Boxer, M. B.; Yamamoto, H. J. Amer. Chem. Soc., 129, 2762-2763 (2007).
30. Enantioselective Route to Platensimycin: An Intramolecular Robinson Annulation Approach. Li, P.; Payette, J.N.; Yamamoto, H. J. Am. Chem. Soc., 129, 9534-9535 (2007).
31. Regioselective and Asymmetric Diels-Alder Reaction of 1- and 2-Substituted Cyclopentadienes Catalyzed by a Brønsted Acid Activated Chiral Oxazaborolidine. Payette, J.N.; Yamamoto, H. J. Am. Chem. Soc., 129, 9536-9537 (2007).
32. Ketone Super Silyl Enol Ethers in Sequential Reactions: Diastereoselective Generation of Tertiary Carbinols in One Pot. Boxer, M.; Yamamoto, H. J. Am. Chem. Soc, 130, 1580-1582 (2008).
33. Catalytic Enantioselective Pudovik Reaction of Aldehydes and Aldimines with Tethers Bis(8-quinolinato) (TBOx) Aluminum Complex. Abell, J. P.; Yamamoto, H. J. Am. Chem. Soc., 130, 10521-10523, (2008).
34. A Brønsted Acid Catalyst for the Enantioselective Protonation Reaction. Cheon, C.H.; Yamamoto, H. J. Am. Chem Soc., 130, 9246-9247, (2008).
35. Stereoselective Synthesis of α,α-Chlorofluoro Carbonyl Compounds Leading to the Construction of Fluorinated Chiral Quaternary Carbon Centers. Shibatomi, K.; Yamamoto, H. Angew. Chem. Int. Ed., 47, 5796-5798, (2008).
36. Catalytic Enantioselective Pudovik Reaction of Aldehydes and Aldimines with Tethers Bis(8-quinolinato) (TBOx) Aluminum Complex. Abell, J. P.; Yamamoto, H. J. Am. Chem. Soc., 130, 10521-10523, (2008).
37. Vanadium-Catalyzed Enantioselective Desymmetrization of meso Secondary Allylic Alcohols and Homoallylic Alcohols. Zhi, L.; Zhang, W.; Yamamoto, H. Angew. Chem. Int. Ed., 47, 7520-7522, (2008).
38. Nitrosobenzene-Mediated C-C Bond Cleavage Reactions and Spectral Observation of an Oxazetidin-4-one Ring System. Payette, J.; Yamamoto, H. J. Amer. Chem. Soc., 130, 12276-12278, (2008).
39. A Sequential O-Nitrosoaldol and Grignard Addition Process: An Enantio- and Diastereoselective Entry to Chiral 1,2 Diols. Jiao, P.; Kawasaki, M.; Yamamoto H. Angew. Chem. Int. Ed., 48, 3333-3336, (2009).
40. Cationic-Oxazaborolidine-Catalyzed Enantioselective Diels-Alder Reaction of α,β-Unsaturated Acetylenic Ketones. Payette, J.N., Yamamoto, H. Angew. Chem. Int. Ed., 48, 8060-8062, (2009).
41. Dual-Activation Asymmetric Strecker Reaction of Aldimines and Ketimines Catalyzed by a Tethered Bis(8-quinolinolato) Aluminum Complex. Abell, J.P.; Yamamoto, H. J. Amer. Chem. Soc., 131, 15118-15119, (2009).
42. Lewis Acid Catalyzed Inverse-Electron-Demand Diels—Alder Reaction of Tropones. Li, P.; Yamamoto, H. J. Amer. Chem. Soc.,131, 16628-16629, (2009).
43. A Triple-Aldol Cascade Reaction for the Rapid Assembly of Polyketides. Albert, B.J.; Yamamoto, H. Angew. Chem. Int. Ed., 49, 2747-2749 (2010).
44. Super Silyl Stereo-Directing Groups for Complete 1,5-Syn and –Anti Stereoselectivities in the Aldol Reactions of -Siloxy Methyl Ketones with Aldehydes. Yamaoka, Y.; Yamamoto. H. J. Am. Chem. Soc., 2010, 132, 5354–5356.
45. Asymmetric Nozaki–Hiyama Propargylation of Aldehydes: Enhancement of Enantioselectivity by Cobalt Co-Catalysis. Usanov, D. L.; Yamamoto, H. Angew. Chem. Int. Ed., 2010, 49, 8169-8172.
46. Zirconium(IV)- and Hafnium(IV)-Catalyzed Highly Enantioselective Epoxidation of Homoallylic and Bishomoallylic Alcohols. Li Z.; Yamamoto, H. J. Am. Chem. Soc., 2010, 132, 7878–7880.
47. Enantioselective Alkynylation of Aldehydes with 1-Haloalkynes Catalyzed by Tethered Bis(8-quinolinato) Chromium Complex, Usanov, D. L.; Yamamoto, H. J. Am. Chem. Soc., 2011, 133, 1286–1289.
48. Iron-Catalyzed Asymmetric Epoxidation of β,β-Disubstituted Enones. Nishikawa, Y., Yamamoto, H. J. Am. Chem. Soc., 2011, 133, 8432-8435.
49. Rapid Total Syntheses Utilizing "Supersilyl" Chemistry Albert, B. J., Yamaoka, Y.; Yamamoto, H. Angew. Chem. Int. Ed., 2011, 50, 2610 -2612.
50. Metal Nitrite: A Powerful Oxidizing Reagent. Baidya, M., Yamamoto. H., J. Am. Chem. Soc., 2011, 133, 13880-13882.
51. Rapid, One-Pot Synthesis of β-Siloxy-α-Haloaldehydes. Saadi, J.; Akakura, M.; Yamamoto, H. J. Am. Chem. Soc., 2011, 133, 14248–14251.