Fun with (4+3)-Cycloadditions

Dedicated to the memory of my parents, Andrew and Bernadine Harmata

Abstract

This account describes how I began my adventure in the area of (4+3)-cycloadditions and then focuses on two ongoing projects: a new catalytic asymmetric (4+3)-cycloaddition and what might be described as the ‘rebirth’ of oxidopyridinium ion (4+3)-cycloaddition chemistry. References to other people’s work are made where appropriate.

1 Introduction

2 Asymmetric, Catalytic (4+3)-Cycloadditions

3 Oxidopyridinium Ions and (4+3)-Cycloadditions

4 Conclusions and the Future

Key words

(4+3)-cycloadditions - sulfones - organocatalysis - oxidopyridinium ions - allylic cations - dienes - asymmetric catalysis

• References and Notes

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Reviews on (4+3)-cycloadditions available in the mid-1980s:
• 3a Mann J. Tetrahedron 1986; 42: 4611
• 3b Hoffmann HM. R. Angew. Chem., Int. Ed. Engl. 1984; 23: 1
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• 4 Harmata M, Gamlath CB. J. Org. Chem. 1988; 53: 6154
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• 6 Harmata M, Sharma U. Org. Lett. 2000; 2: 2703
• 7a Harmata M, Rashatasakhon P. Org. Lett. 2000; 2: 2913
• 7b Harmata M, Elomari S, Barnes CL. J. Am. Chem. Soc. 1996; 118: 2860
• 7c Harmata M, Elahmad S, Barnes CL. J. Org. Chem. 1994; 59: 1241
• 8a Harmata M, Wacharasindhu S. Org. Lett. 2005; 7: 2563
• 8b Harmata M, Bohnert GJ. Org. Lett. 2003; 5: 59
• 8c Harmata M, Rashatasakhon P. Org. Lett. 2001; 3: 2533
• 8d Harmata M, Shao L. Synthesis 1999; 1534
• 9a Harmata M, Lee DR, Barnes CL. Org. Lett. 2005; 7: 1881
• 9b Harmata M, Lee DR. J. Am. Chem. Soc. 2002; 124: 14328
• 10a Harmata M, Kahraman M, Adenu G, Barnes CL. Heterocycles 2004; 62: 583
• 10b Harmata M, Carter KW. Tetrahedron Lett. 1997; 38: 7985
• 11 Harmata M, Gomes MG. Eur. J. Org. Chem. 2006; 2273
• 12a Harmata M, Brackley JA, Barnes CL. Tetrahedron Lett. 2006; 47: 8151
• 12b Harmata M, Ghosh SK, Hong X, Wacharasindhu S, Kirchhoefer P. J. Am. Chem. Soc. 2003; 125: 2058
• 13a Huang J, Hsung RP. J. Am. Chem. Soc. 2005; 127: 50
• 13b Villar L, Uria U, Martinez JI, Prieto L, Reyes E, Carrillo L, Vicario JL. Angew. Chem. Int. Ed. 2017; 56: 10535
• 13c Banik SM, Levina A, Hyde AM, Jacobsen EN. Science 2017; 358: 761
• 13d Gelis C, Levitre G, Merad J, Retailleau P, Neuville L, Masson G. Angew. Chem. Int. Ed. 2018; 57: 12121
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• 15d Sun W.-B, Wang X, Sun B.-F, Zou J.-P, Lin G.-Q. Org. Lett. 2016; 18: 1219
• 16 Krenske EH, Houk KN, Harmata M. J. Org. Chem. 2015; 80: 744
• 17a Harmata M, Zheng P, Schreiner PR, Navarro-Vazquez A. Angew. Chem. Int. Ed. 2006; 45: 1966
• 17b Harmata M, Rayanil K.-O. Synthesis 2007; 2370
• 17c Harmata M, Zheng P, Schreiner PR, Navarro-Vazquez A. Tetrahedron Lett. 2007; 48: 5919
• 17d Thomas JB, Waas JR, Harmata M, Singleton DA. J. Am. Chem. Soc. 2008; 130: 14544
• 18 ‘Yet hope remains while the company is true’; the word has been used by at least one other: Dong S, Qin T, Hamel E, Beutler JA, Porco JA. J. Am. Chem. Soc. 2012; 134: 19782
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• 21 Harmata M, Bohnert G, Barnes CL. Tetrahedron Lett. 2001; 42: 149

Selected reviews include:
• 22a Yu B. Acc. Chem. Res. 2018; 51: 507
• 22b Gu Y, Tan C, Gong J, Yang Z. Synlett 2018; 29: 1552
• 22c Quach R, Furkert DP, Brimble MA. Org. Biomol. Chem. 2017; 15: 3098
• 22d Echavarren AM, Hashmi AS. K, Toste FD. Adv. Synth. Catal. 2016; 358: 1347
• 23 Aikawa H, Tago S, Umetsu K, Haginiwa N, Asao N. Tetrahedron 2009; 65: 1774
• 24 Topinka M, Tata RR, Harmata M. Org. Lett. 2014; 16: 4476
• 25 Harding AP, Wedge DC, Popelier PL. A. J. Chem. Inf. Model. 2009; 49: 1914
• 26 Scherrer RA, Donovan SF. Anal. Chem. 2009; 81: 2768
• 27a Jain P, Wang H, Houk KN, Antilla JC. Angew. Chem. Int. Ed. 2012; 51: 1391
• 27b Zhang Z, Antilla JC. Angew. Chem. Int. Ed. 2012; 51: 11778
• 27c Zhang Z, Jain P, Antilla JC. Angew. Chem. Int. Ed. 2011; 50: 10961
• 28 He H, Chen L.-Y, Wong W.-Y, Chan W.-H, Lee AW. M. Eur. J. Org. Chem. 2010; 4181
• 29 Liu C, Oblak EZ, Vander Wal MN, Dilger AK, Almstead DK, MacMillan DW. C. J. Am. Chem. Soc. 2016; 138: 2134
• 30 Topinka M, Zawatzky K, Barnes CL, Welch CJ, Harmata M. Org. Lett. 2017; 19: 4106
• 31 He CQ, Yu P, Lam Y.-H, Houk KN. Org. Lett. 2017; 19: 5685
• 32 Dennis N, Ibrahim B, Katritzky AR. J. Chem. Soc., Perkin Trans. 1 1976; 2307
• 33 Dennis N, Ibrahim B, Katritzky AR. J. Chem. Soc., Perkin Trans. 1 1976; 2296
• 34 Dennis N, Katritzky AR, Rittner R. J. Chem. Soc., Perkin Trans. 1 1976; 2329
• 35a Bejcek LP, Murelli RP. Tetrahedron 2018; 74: 2501
• 35b Pellissier H. Adv. Synth. Catal. 2011; 353: 189
• 35c Singh V, Krishna UM, Vikrant Trivedi GK. Tetrahedron 2008; 64: 3405
• 36 Sammes PG, Street LJ. J. Chem. Soc., Perkin Trans. 1 1983; 1261
• 37 Harmata M, Bohnert GJ. Org. Lett. 2003; 5: 59
• 38a Ess DH, Wheeler SE, Iafe RG, Xu L, Celebi-Olcum N, Houk KN. Angew. Chem. Int. Ed. 2008; 47: 7592
• 38b Thomas JB, Waas JR, Harmata M, Singleton DA. J. Am. Chem. Soc. 2008; 130: 14544
• 38c Quadrelli P, Romano S, Toma L, Caramella P. J. Org. Chem. 2003; 68: 6035
• 38d Caramella P, Quadrelli P, Toma L. J. Am. Chem. Soc. 2002; 124: 1130
• 39 https://faculty.missouri.edu/~harmatam/fund.shtml
• 40 Shirakawa S, Maruoka K. Angew. Chem. Int. Ed. 2013; 52: 4312
• 41 A reviewer called this Account ‘…amazingly self-indulgent.’ But I did try to tone things down a bit; I took out the reference to Sister Mary Anne. In any case, I have been called much worse. I have attempted to humanize the scientific experience in this essay. Whether it offends, is considered unprofessional, or just completely fails, well, that is a chance I am willing to take. Another reviewer probably knew me well enough to recognize that there is method in the madness. Interestingly, while some relatives lauded the work; one described it as a ‘pity party’. All of this is of interest to me. Whom does one try to please when writing?