Design of Highly Functional Small-Molecule Catalysts and Related Reactions Based on Acid-Base Combination Chemistry

Abstract

The design of small but highly functional artificial catalysts is very important for practical organic synthesis. We have ­succeeded in the rational design of small and simple catalysts and related reactions based on acid-base combination chemistry. Acid-base combined catalysts can be classified into three types: (i) acid-base combined salt catalysts, (ii) conjugate acid-base catalysts, and (iii) nonconjugate acid-base catalysts. We have systematically developed acid-base combined salt catalysts such as ammonium salts, ate complexes, ion pairs and cation-π complexes, acid-base conjugate catalysts such as metal oxides (monoconjugation) and zinc(II)-3,3′-diphosphinol-BINOLates (triconjugation), and acid-base nonconjugate catalysts like l-histidine-derived sulfonamides.

• 1 Introduction

• 2 General Concept for the Design of Catalysts Based on Acid-Base Combination Chemistry

• 3 Catalytic Dehydrative Monoesterification of Phosphoric Acid with Alcohols Based on Acid-Base Combination Chemistry

• 4 Acid-Base Combined Salt Catalysts (Type A)

• 4.1 Brønsted Acid-Brønsted Base Combined Salt Catalysts (Type A-1)

• 4.2 Lewis Acid-Lewis Base Combined Salt Catalysts and Reagents (Type A-2)

• 4.3 Cation-Anion-Pair Catalysts (Type A-3)

• 4.4 Cation-π Complex Catalysts (Type A-4)

• 5 Lewis Acid-Lewis Base Conjugate Catalysts (Type B)

• 5.1 Molybdenum Oxides as Highly Effective Dehydrative ­Cyclization Catalysts Directed toward the Synthesis of ­Oxazolines and Thiazolines (Type B-1)

• 5.2 Zinc(II)-3,3"-Diphosphinoyl-BINOLates in the ­Asymmetric Addition of Organozinc Reagents to ­Aldehydes (Type B-2)

• 6 Brønsted Acid-Lewis Base Nonconjugate Asymmetric Catalysts (Separated Type) (Type C)

• 6.1 l-Histidine-derived Sulfonamide as a Minimal Artificial Acylase for the Kinetic Resolution of Racemic Alcohols

• 7 Conclusions

Key words

catalysis - salt - conjugate - acid-base combination chemistry - asymmetric synthesis

References and Notes

• 1 Artificial Enzymes   Breslow R. Wiley-VCH; Weinheim: 2005. 
• 2 For examples of Lewis acid-Lewis base bifunctional asymmetric catalysis, see: Kanai M. Kato N. Ichikawa E. Shibaski M. Synlett  2005,  1491 
• 3 Sakakura A. Katsukawa M. Ishihara K. Org. Lett.  2005,  7:  1999 
• For reviews, see:
• 4a Hayakawa Y. In Comprehensive Organic Synthesis   Vol. 6:  Trost BM. Fleming I. Winterfeldt E. Pergamon; Oxford: 1991.  p.601-630  
• 4b Resse CB. Org. Biomol. Chem.  2005,  3:  3851 
• 5 2′,3′-O-Isopropylidiene ribonucleoside 5′-monophosphates were synthesized from the corresponding ribonucleosides and 5 equiv of phosphoric acid in the presence of 10 equiv of Bu₃N under reflux in DMF (153 °C) in moderate yield (38-58%). See: Honjo M. Furukawa Y. Kobayashi K. Chem. Pharm. Bull.  1966,  14:  1061 
• 6a Ishihara K. Nakagawa S. Sakakura A. J. Am. Chem. Soc.  2005,  127:  4168 
• 6b Sakakura A. Nakagawa S. Ishihara K. Tetrahedron  2006,  62:  422 
• 7 Otera J. Esterification   Wiley-VCH; Weinheim: 2003. 
• 8 Wakasugi K. Misaki T. Yamada K. Tanabe Y. Tetrahedron Lett.  2000,  41:  5249 
• Hafnium(IV) and zirconium(IV) salts (0.10-1.0 mol%) are highly effective catalysts for the ester condensation reaction of carboxylic acids with equimolar amounts of alcohols. In their method azeotropic reflux conditions with the removal of water are required to form the corresponding ester in excellent yield. See:
• 9a Ishihara K. Ohara S. Yamamoto H. Science  2000,  390:  1140 
• 9b Ishihara K. Nakayama M. Ohara S. Yamamoto H. Synlett  2001,  1117 
• 9c Ishihara K. Nakayama M. Ohara S. Yamamoto H. Tetrahedron  2002,  58:  8179 
• 9d Nakayama M. Sato A. Ishihara K. Yamamoto H. Adv. Synth. Catal.  2004,  346:  1275 
• 9e Sato A. Nakamura Y. Maki T. Ishihara K. Yamamoto H. Adv. Synth. Catal.  2005,  347:  1337 
• 9f Nakamura Y. Maki T. Ishihara K. Yamamoto H. Adv. Synth. Catal.  2006,  348:  1505 
• 11a Ishihara K. Nakano K. J. Am. Chem. Soc.  2005,  127:  10504 
• 11b Ishihara K. Nakano K. J. Am. Chem. Soc.  2005,  127:  13079 ; additions and corrections
• 12a Sakakura A. Suzuki K. Nakano K. Ishihara K. Org. Lett.  2006,  8:  2229 
• 12b Sakakura A. Suzuki K. Ishihara K. Adv. Synth. Catal.  2006,  348:  2457 
• 13a Ahrendt K. Borths CJ. MacMillan DW. J. Am. Chem. Soc.  2000,  122:  4243 
• 13b Northrup AB. MacMillan DWC. J. Am. Chem. Soc.  2002,  124:  2458 
• 14a Corey EJ. Loh T.-P. J. Am. Chem. Soc.  1991,  113:  8966 
• 14b Ishihara K. Gao Q. Yamamoto H. J. Org. Chem.  1993,  58:  6917 
• 14c Ishihara K. Yamamoto H. J. Am. Chem. Soc.  1994,  116:  1561 
• 14d Ishihara K. Kurihara H. Yamamoto H. J. Am. Chem. Soc.  1996,  118:  3049 
• 14e Ishihara K. Kurihara H. Matsumoto M. Yamamoto H. J. Am. Chem. Soc.  1998,  120:  6920 
• 15 Hatano M. Matsumura T. Ishihara K. Org. Lett.  2005,  7:  573 
• 16 Hatano M. Suzuki S. Ishihara K. J. Am. Chem. Soc.  2006,  128:  9998 
• 17a Imamoto T. Sugiura Y. Takiyama N. Tetrahedron Lett.  1984,  38:  4233 
• 17b Imamoto T. Takiyama N. Nakamura K. Tetrahedron Lett.  1985,  39:  4763 
• 17c Imamoto T. Takiyama N. Nakamura K. Hatajima T. Kamiya Y. J. Am. Chem. Soc.  1989,  111:  4392 
• 18 Ishihara K. Yano T. Org. Lett.  2004,  6:  1983 
• For reviews, see:
• 19a Hamlin KE. Weston AW. Org. React.  1957,  9:  1 
• 19b Paquette LA. Gilday JP. Org. Prep. Proced. Int.  1990,  22:  167 
• 19c Mehta G. Venkateswaran RV. Tetrahedron  2000,  56:  1399 
• 20 Hatano M. Ikeno T. Miyamoto T. Ishihara K. J. Am. Chem. Soc.  2005,  127:  10776 
• 21a Holmes IP. Kagan HB. Tetrahedron Lett.  2000,  41:  7453 
• 21b Holmes IP. Kagan HB. Tetrahedron Lett.  2000,  41:  7457 
• 22 Ishihara K. Fushimi M. Org. Lett.  2006,  8:  1921 
• 23a Otto S. Boccaletti G. Engberts JBFN. J. Am. Chem. Soc.  1998,  120:  4328 
• 23b Otto S. Engberts JBFN. J. Am. Chem. Soc.  1999,  121:  6798 
• 24a van der Helm D. Lawson MB. Enwall EL. Acta Crystallogr., Sect. B  1972,  28:  2307 
• 24b Muhonen H. Hämäläinen R. Finn. Chem. Lett.  1983,  120 
• 25a Yamada S. Morita C. J. Am. Chem. Soc.  2002,  124:  8184 
• 25b Yamada S. Misono T. Iwai Y. Tetrahedron Lett.  2005,  46:  2239 
• 26 Johnson JS. Evans DA. Acc. Chem. Res.  2000,  33:  325 
• 27 Sakakura A. Kondo R. Ishihara K. Org. Lett.  2005,  7:  1971 
• 28 Velusamy S. Ahamed M. Punniyamurthy T. Org. Lett.  2004,  6:  4821 
• 29a Hatano M. Miyamoto T. Ishihara K. Adv. Synth. Catal.  2005,  347:  1561 
• 29b Hatano M. Miyamoto T. Ishihara K. Synlett  2006,  1762 
• 29c Hatano M. Miyamoto T. Ishihara K. J. Org. Chem.  2006,  71:  6474 
• 30 Hatano M. Miyamoto T. Ishihara K. Curr. Org. Chem.  2007,  11:  127 
• 31a Kitamura M. Suga S. Kawai K. Noyori R. J. Am. Chem. Soc.  1986,  108:  6071 
• 31b Noyori R. Kitamura M. Angew. Chem., Int. Ed. Engl.  1991,  30:  40 
• 32a Mori M. Nakai T. Tetrahedron Lett.  1997,  38:  6233 
• 32b Zhang F.-Y. Yip C.-W. Cao R. Chan ASC. Tetrahedron: Asymmetry  1997,  8:  585 
• 32c Balsells J. Davis TJ. Carroll P. Walsh PJ. J. Am. Chem. Soc.  2002,  124:  10336 
• 33a Huang W.-S. Hu Q.-S. Pu L. J. Org. Chem.  1998,  63:  1364 
• 33b Simonson DL. Kingsbury K. Xu M.-H. Hu Q.-S. Sabat M. Pu L. Tetrahedron  2002,  58:  8189 
• 33c Qin Y.-C. Pu L. Angew. Chem. Int. Ed.  2006,  45:  273 
• 34 Ishihara K. Kosugi Y. Akakura M. J. Am. Chem. Soc.  2004,  126:  12212 
• 35 Vedejs E. Chen X. J. Am. Chem. Soc.  1996,  118:  1809 
• 36a Ruble JC. Latham HA. Fu GC. J. Am. Chem. Soc.  1997,  119:  1492 
• 36b Kawabata T. Nagato M. Takasu K. Fuji K. J. Am. Chem. Soc.  1997,  119:  3169 
• 36c Spivey AC. Fekner T. Spay SE. J. Org. Chem.  2000,  65:  3154 
• 36d Naraku G. Shimomoto N. Hanamoto T. Inanaga J. Enantiomer  2000,  5:  135 
• 36e Priem G. Pelotier B. Macdonald SJF. Anson MS. Campbell IB. J. Org. Chem.  2003,  68:  3844 
• 37a Miller SJ. Copeland GT. Papaioannou N. Horstmann TE. Ruel EM. J. Am. Chem. Soc.  1998,  120:  1629 
• 37b Vasbinder MM. Jarvo ER. Miller SJ. Angew. Chem. Int. Ed.  2001,  40:  2824 

10

We have observed the similar unusual rate-accelerating effect in the dehydrative cyclization of 1,3,5-triketones to γ-pyrones catalyzed by bulky diarylammonium pentafluoro-benzenesulfonates. These results more strongly suggested a hydrophobic effect of catalysts. See: Sakakura, A.; Watanabe, H.; Nakagawa, S.; Ishihara, K.; to be submitted