Thieme Chemistry Journal Awardees - Where Are They Now? Triflic Imide Catalyzed Cycloaddition Reactions

Abstract

This Account summarizes our recent development of triflic imide (Tf₂NH)-catalyzed cycloaddition and cascade reactions. Reactions of electron-rich olefins, possessing a silyl group, with α,β-unsaturated carbonyl compounds afforded highly substituted cyclobutanes, cyclopentanes, and bicyclo[4.2.0]octanes in good to excellent yields. In the reactions, Tf₂NH acts as a precatalyst to produce a strong Lewis acid, silyl triflic imide, which activates the cycloaddition reactions. Reactions of electron-rich olefins with aldimines furnished highly substituted heterocycles such as piperidines, quinolines, and pyrrolidines. In these cases, Tf₂NH acts as a strong Brønsted acid. Moreover, it was found that Tf₂NH can catalyze more than two mechanistically distinct reactions in one pot (tandem catalysis), so that a variety of molecular skeletons can be constructed in a single operation.

1 Introduction

2 (2+2) Cycloaddition of α,β-Unsaturated Esters

2.1 (2+2) Cycloadditon with Silyl Enol Ethers

2.2 (2+2) Cycloaddition with Allylsilanes

3 (3+2) Cycloaddition of Donor-Acceptor Cyclopropanes

4 Multicomponent Reaction: Cascade (4+2)-(2+2) Cycloaddition

5 Cycloaddition of Imines

5.1 Aza-(4+2) Cycloaddition with 2-Siloxydienes

5.2 Cascade Povarov-Hydrogen-Transfer Reaction with Allylsilanes

5.3 Aza-(3+2) Cycloaddition with α,α-Dimethylallylsilanes

6 Conclusions

Key words

cycloadditions - catalysis - multicomponent reactions - triflic imides - auto-tandem catalysis

References and Notes

• 1a Carruthers W. Cycloaddition Reactions in Organic Synthesis   Pergamon Press; Oxford: 1990. 
• 1b Cycloaddition Reactions in Organic Synthesis   Kobayashi S. Jørgensen KA. Wiley-VCH; Weinheim: 2002. 
• 3 Lewis Acids in Organic Synthesis   Vol. 1 and 2:  Yamamoto H. Wiley-VCH; Weinheim: 2000. 
• 4 Yamamoto H. Nakashima D. In Acid Catalysis in Modern Organic Synthesis   Yamamoto H. Ishihara K. Wiley-VCH; Weinheim: 2008.  p.35 
• 5 Akiyama T. Chem. Rev.  2007,  107:  5744 
• 6 Foropoulos J. DesMarteau DD. Inorg. Chem.  1984,  23:  3720 
• 7a Ishihara K. Hiraiwa Y. Yamamoto H. Synlett  2001,  1851 
• 7b Cossy J. Lutz F. Alauze V. Meyer C. Synlett  2002,  45 
• 7c Boxer MB. Yamamoto H. J. Am. Chem. Soc.  2006,  128:  48 
• 7d Boxer MB. Yamamoto H. Nat. Protoc.  2006,  1:  2434 
• 7e Boxer MB. Yamamoto H.
  J. Am. Chem. Soc.  2007,  129:  2762 
• 7f Boxer MB. Akakura M. Yamamoto H. J. Am. Chem. Soc.  2008,  130:  1580 
• 8 Othman RB. Bousquet T. Othman M. Dalla V. Org. Lett.  2005,  7:  5335 
• 9a Nakashima D. Yamamoto H. Org. Lett.  2005,  7:  1251 
• 9b Jung ME. Ho DG. Org. Lett.  2007,  9:  375 
• 10 Kawamura M. Cui D.-M. Shimada S. Tetrahedron  2006,  62:  9201 
• 11a Zhang L. Kozmin SA. J. Am. Chem. Soc.  2004,  126:  10204 
• 11b Sun J. Kozmin SA. J. Am. Chem. Soc.  2005,  127:  13512 
• 11c Zhang Y. Hsung RP. Zhang X. Huang J. Slafer BW. Davis A. Org. Lett.  2005,  7:  1047 
• 11d Yu SH. Ferguson MJ. McDonald R. Hall DG. J. Am. Chem. Soc.  2005,  127:  12808 
• 11e Hashimoto T. Naganawa Y. Kano T. Maruoka K. Chem. Commun.  2007,  5143 
• 11f Ko C. Feltenberger JB. Ghosh SK. Hsung RP. Org. Lett.  2008,  10:  1971 
• 12a Baldwin JE. In Comprehensive Organic Synthesis   Vol. 5:  Trost BM. Fleming I. Pergamon Press; Oxford: 1991.  p.63 
• 12b Lee-Ruff E. Mladenova G. Chem. Rev.  2003,  103:  1449 
• 13 Crimmins MT. In Comprehensive Organic Synthesis   Vol. 5:  Trost BM. Pergamon Press; Oxford: 1991.  p.123 
• 14a Ulrich H. Cycloaddition Reactions of Heterocumulenes   Academic Press; London: 1967. 
• 14b Ahmad S. Tetrahedron Lett.  1991,  32:  6997 
• 15 Narasaka K. Hayashi Y. Shimadzu H. Niihata S. J. Am. Chem. Soc.  1992,  114:  8869 
• 16 Yamazaki S. Kumagai H. Yamabe S. Yamamoto K. J. Org. Chem.  1998,  63:  3371 
• 17a Takasu K. J. Pharm. Soc. Jpn.  2001,  121:  887 
• 17b Ihara M. Chem. Pharm. Bull.  2006,  54:  765 
• 17c Takasu K. J. Synth. Org. Chem. Jpn.  2008,  66:  554 
• 18a Clark RD. Untch KG. J. Org. Chem.  1979,  44:  253 
• 18b Magnus P. Rigollier P. Lacour J. Tobler H. J. Am. Chem. Soc.  1992,  114:  3993 
• 18c Sweis RF. Schramm MP. Kozmin SA. J. Am. Chem. Soc.  2004,  126:  7442 
• 18d Ishihara K. Nakano K. J. Am. Chem. Soc.  2007,  129:  1746 
• 19a Takasu K. Ueno M. Inanaga K. Ihara M. J. Org. Chem.  2004,  69:  517 
• 19b Takasu K. Nagao S. Ueno M. Ihara M. Tetrahedron  2004,  60:  2071 
• 19c Takasu K. Nagao S. Ihara M. Tetrahedron Lett.  2005,  46:  1005 
• 20a Boxer MB. Yamamoto H. Org. Lett.  2005,  7:  3127 
• 20b Avenoza A. Busto JH. Canal N. Peregnina JM. Perez-Fernandez M. Org. Lett.  2005,  7:  3597 
• 20c Canales E. Corey EJ. J. Am. Chem. Soc.  2007,  129:  12686 
• 21 Inanaga K. Takasu K. Ihara M. J. Am. Chem. Soc.  2005,  127:  3668 
• 22a Ayer WA. Saeedi-Ghomi MH. Can. J. Chem.  1981,  59:  2536 
• 22b Clericuzio M. Mella M. Toma L. Finzi PV. Vidari G. Eur. J. Org. Chem.  2002,  988 
• Examples of Lewis acid promoted (2+2) cycloadditions of activated alkynes:
• 23a Snider BB. Roush DM. J. Am. Chem. Soc.  1979,  101:  5283 
• 23b Franck-Neumann M. Miesch M. Gross L. Tetrahedron Lett.  1992,  33:  3879 
• 23c Miesch M. Wendling F. Eur. J. Org. Chem.  2000,  381 
• 24 Takasu K. Ishii T. Inanaga K. Ihara M. Org. Synth.  2006,  83:  193 
• 25a Mathieu B. Ghosez L. Tetrahedron Lett.  1997,  38:  5497 
• 25b Ishii A. Kotera O. Saeki T. Mikami K. Synlett  1997,  1145 
• 25c Mathieu B. Ghosez L. Tetrahedron  2002,  58:  8219 
• 26 Takasu K. Miyakawa Y. Ihara M. Tokuyama H. Chem. Pharm. Bull.  2008,  56:  1205 
• 27 Takasu K. Hosokawa N. Inanaga K. Ihara M. Tetrahedron Lett.  2006,  47:  6053 
• Knölker et al. reported that (2+2) cycloadditions of allylsilanes with α,β-unsaturated esters are promoted by stoichiometric amounts of TiCl₄:
• 28a Knölker H.-J. Baum G. Graf R. Angew. Chem., Int. Ed. Engl.  1994,  33:  1612 
• 28b Knölker H.-J. Baum E. Schmitt O. Tetrahedron Lett.  1998,  39:  7705 
• 28c Organ MG. Dragan V. Miller M. Froese RDJ. Goddard JD. J. Org. Chem.  2000,  65:  3666 
• 29a Reissig H.-U. Zimmer R. Chem. Rev.  2003,  103:  1151 
• 29b Yu M. Pagenkopf BL. Tetrahedron  2005,  61:  321 
• 30a Komatusu M. Suehiro I. Horiguchi Y. Kuwajima I. Synlett  1991,  771 
• 30b Horiguchi Y. Suehiro I. Sasaki A. Kuwajima I. Tetrahedron Lett.  1993,  34:  6077 
• 30c Yadav VK. Sriramurthy V. Angew. Chem. Int. Ed.  2004,  43:  2669 
• 31 Takasu K. Nagao S. Ihara M. Adv. Synth. Catal.  2006,  348:  2376 
• 32 Multicomponent Reactions   Zhu J. Bienaymé H. Wiley-VCH; Weinheim: 2005. 
• 33a Ulaczyk-Lsesanko A. Hall DG. Curr. Opin. Chem. Biol.  2005,  9:  266 
• 33b Zhu J. Eur. J. Org. Chem.  2003,  1133 
• 33c Ugi I. Pure Appl. Chem.  2001,  73:  187 
• 33d Dömling A. Chem. Rev.  2006,  106:  17 
• 34 Inanaga K. Takasu K. Ihara M. J. Am. Chem. Soc.  2004,  126:  1352 
• 35 Definition of ‘auto-tandem catalysis’: Fogg DE. dos Santos EN. Coord. Chem. Rev.  2004,  248:  2365 
• 36 Wasilke J.-C. Obrey SJ. Baker RT. Bazan GC. Chem. Rev.  2005,  105:  1001 
• Recent representative examples for an auto-tandem catalysis:
• 37a Field LD. Messerle BA. Wren SL. Organometallics  2003,  22:  4393 
• 37b Du H. Zhang X. Wang Z. Ding K. Tetrahedron  2005,  61:  9465 
• 37c Enders D. Hüttl MRM. Grondal C. Raabe G. Nature (London)  2006,  441:  861 
• 37d Shekhar S. Trantow B. Leitner A. Hartwig JF. J. Am. Chem. Soc.  2006,  128:  11770 
• 38 Brasco MFR. Seldes AM. Palermo JA. Org. Lett.  2001,  3:  1415 
• 39 Takasu K. Inanaga K. Ihara M. Tetrahedron Lett.  2008,  49:  4220 
• 40 Boger DL. Weinreb SM. Hetero Diels-Alder Methodology in Organic Synthesis   Academic Press; San Diego: 1987. 
• 41 Takasu K. Shindoh N. Tokuyama H. Ihara M. Tetrahedron  2006,  62:  11900 
• 42 Povarov LS. Russ. Chem. Rev.  1967,  36:  656 
• 43a Shindoh N. Tokuyama H. Takasu K. Tetrahedron Lett.  2007,  48:  4749 
• 43b Shindoh N. Tokuyama H. Takemoto Y. Takasu K. J. Org. Chem.  2008,  73:  7451 
• 44 Shindoh N. Tokuyama H. Takemoto Y. Takasu K. Heterocycles  2009,  77:  187 

2

Two systems of notations, (i+j+…) and [i+j+…], have been used for cycloaddition reactions; see the IUPAC guides for their difference. A (i+j+…) cycloaddition is a reaction in which two or more molecules provide units of i, j, … linearly connected atoms: these units become joined at their respective termini by new s bond so as to form a cyclic compound containing (i+j+…) atoms. In contrast, the symbolism [i+j+…] for a cycloaddition identifies the numbers i, j, … of electrons in the interacting units that participate in the transformation of reactants to products. In this Letter, the symbolism (i+j+…) will be used. See IUPAC Gold Book (http://goldbook.iupac.org/index.html).