50 Years of Zweifel Olefination: A Transition-Metal-Free Coupling

Dedicated to Professor Herbert Mayr on the occasion of his 70^th birthday

Abstract

The Zweifel olefination is a powerful method for the stereoselective synthesis of alkenes. The reaction proceeds in the absence of a transition-metal catalyst, instead taking place by iodination of vinyl boronate complexes. Pioneering studies into this reaction were reported in 1967 and this short review summarizes developments in the field over the past 50 years. An account of how the Zweifel olefination was modified to enable the coupling of robust and air-stable boronic esters is presented followed by a summary of current state of the art developments in the field, including stereodivergent olefination and alkynylation. Finally, selected applications of the Zweifel olefination in target-oriented synthesis are reviewed.

1 Introduction

2.1 Zweifel Olefination of Vinyl Boranes

2.2 Zweifel Olefination of Vinyl Borinic Esters

2.3 Extension to Boronic Esters

3.1 Introduction of an Unsubstituted Vinyl Group

3.2 Coupling of α-Substituted Vinyl Partners

3.3 Syn Elimination

4 Zweifel Olefination in Natural Product Synthesis

5 Conclusions and Outlook

Key words

Zweifel olefination - coupling - boronic esters - alkenes - transition­-metal-free - enantiospecific

• References

• 1a Stereoselective Alkene Synthesis. In Topics in Current Chemistry,. Vol. ■■?■■. Wang J. Springer; Heidelberg: 2012
• 1b Williams JM. J. Preparation of Alkenes: A Practical Approach . Oxford University Press; Oxford: 1996
• 1c Negishi E. Huang Z. Wang G. Mohan S. Wang C. Hattori H. Acc. Chem. Res. 2008; 41: 1474
• 2a Miyaura N. Suzuki A. Chem. Rev. 1995; 95: 2457
• 2b Chemler SR. Trauner D. Danishefsky SJ. Angew. Chem. Int. Ed. 2001; 40: 4544
• 2c Nicolaou KC. Bulger PG. Sarlah D. Angew. Chem. Int. Ed. 2005; 44: 4442
• 2d Jana R. Pathak TP. Sigman MS. Chem. Rev. 2011; 111: 1417
• 2e Suzuki A. Angew. Chem. Int. Ed. 2011; 50: 6722
• 2f Li J. Ballmer SG. Gillis EP. Fujii S. Schmidt MJ. Palazzolo AM. E. Lehmann JW. Morehouse GF. Burke MD. Science 2015; 347: 1221
• 2g Thomas AA. Denmark SE. Science 2016; 352: 329
• 3a Leonori D. Aggarwal VK. Angew. Chem. Int. Ed. 2015; 54: 1082
• 3b Wang C.-Y. Derosa J. Biscoe MR. Chem. Sci. 2015; 6: 5105
• 3c Cherney AH. Kadunce NT. Reisman SE. Chem. Rev. 2015; 115: 9587
• 3d Lee JC. H. McDonald R. Hall DG. Nat. Chem. 2011; 3: 894
• 4 Sun C.-L. Shi Z.-J. Chem. Rev. 2014; 114: 9219

For other review articles which discuss Zweifel olefination, see:
• 5a Matteson DS. Chem. Rev. 1989; 89: 1535
• 5b Matteson DS. J. Organomet. Chem. 1999; 581: 51
• 5c Scott HK. Aggarwal VK. Chem. Eur. J. 2011; 17: 13124
• 5d Leonori D. Aggarwal VK. Acc. Chem. Res. 2014; 47: 3174
• 5e Sandford C. Aggarwal VK. Chem. Commun. 2017; 53: 5481
• 6 Zweifel G. Arzoumanian H. Whitney CC. J. Am. Chem. Soc. 1967; 89: 3652
• 7 Zweifel G. Fisher RP. Snow JT. Whitney CC. J. Am. Chem. Soc. 1971; 93: 6309
• 8 Matteson DS. Liedtke JD. J. Am. Chem. Soc. 1965; 87: 1526
• 9 For the synthesis of trisubstituted alkenes, see: Brown HC. Basavaiah D. Kulkarni SU. J. Org. Chem. 1982; 47: 171
• 10 Zweifel G. Fisher RP. Snow JT. Whitney CC. J. Am. Chem. Soc. 1972; 94: 6560
• 11 LaLima NJ. Levy AB. J. Org. Chem. 1978; 43: 1279
• 12 Suzuki A. Miyaura N. Abiko S. Itoh M. Brown HC. Sinclair JA. Midland MM. J. Am. Chem. Soc. 1973; 95: 3080

For selected examples of alkynylation of boranes and borinic esters, see:
• 13a Negishi E. Lew G. Yoshida T. J. Chem. Soc., Chem. Commun. 1973; 22: 874
• 13b Suzuki A. Miyaura N. Abiko S. Itoh M. Midland MM. Sinclair JA. Brown HC. J. Org. Chem. 1986; 51: 4507
• 13c Naruse M. Utimoto K. Nozaki H. Tetrahedron 1974; 30: 2159
• 13d Naruse M. Utimoto K. Nozaki H. Tetrahedron Lett. 1973; 14: 2741
• 13e Pelter A. Drake RA. Tetrahedron Lett. 1988; 29: 4181
• 13f Sikorski JA. Bhat NG. Cole TE. Wang KK. Brown HC. J. Org. Chem. 1986; 51: 4521
• 13g Canterbury DP. Micalizio GC. J. Am. Chem. Soc. 2010; 132: 7602
• 14a Aggarwal VK. Fang GY. Ginesta X. Howells DM. Zaja M. Pure Appl. Chem. 2006; 78: 215
• 14b Slayden SW. J. Org. Chem. 1981; 46: 2311
• 14c Slayden SW. J. Org. Chem. 1982; 47: 2753
• 15 Zweifel G. Polston NL. Whitney CC. J. Am. Chem. Soc. 1968; 90: 6243
• 16a Tripathy PB. Matteson DS. Synthesis 1990; 200
• 16b Elliott MC. Smith K. Jones DH. Hussain A. Saleh BA. J. Org. Chem. 2013; 78: 3057
• 17a Brown HC. Basavaiah D. J. Org. Chem. 1982; 47: 3806
• 17b Brown HC. Basavaiah D. J. Org. Chem. 1982; 47: 5407
• 17c Brown HC. Basavaiah D. Kulkarni SU. Bhat NG. Prasad JV. N. V. J. Org. Chem. 1988; 53: 239
• 18a For a review see: Collins BS. L. Wilson CM. Myers EL. Aggarwal VK. Angew. Chem. Int. Ed. 2017;

For selected recent examples, see:
• 18b Schmidt J. Choi J. Liu AT. Slusarczyk M. Fu GC. Science 2016; 354: 1265
• 18c Zhang L. Lovinger GJ. Edelstein EK. Szymaniak AA. Chierchia MP. Morken JP. Science 2016; 351: 70
• 18d Li C. Wang J. Barton LM. Yu S. Tian M. Peters DS. Kumar M. Yu AW. Johnson KA. Chatterjee AK. Yan M. Baran PS. Science 2017;
• 19a Matteson DS. Jesthi PK. J. Organomet. Chem. 1976; 110: 25
• 19b Matteson had previously described this work in a review article: Matteson DS. Synthesis 1975; 147
• 20a Evans DA. Thomas RC. Walker JA. Tetrahedron Lett. 1976; 17: 1427
• 20b Evans DA. Crawford TC. Thomas RC. Walker JA. J. Org. Chem. 1976; 41: 3947
• 21 Brown HC. Bhat NG. J. Org. Chem. 1988; 53: 6009

For selected applications of Zweifel reactions of boranes and borinic esters, see:
• 22a Abatjoglou AG. Portoghese PS. Tetrahedron Lett. 1976; 17: 1457
• 22b Kulkarni UU. Basavaiah D. Brown HC. J. Organomet. Chem. 1982; 225: C1
• 22c Basavaiah D. Brown HC. J. Org. Chem. 1982; 47: 1792
• 22d Mikhailov BM. Gurskii ME. Pershin DG. J. Organomet. Chem. 1983; 246: 19
• 22e Hyuga S. Takinami S. Hara S. Suzuki A. Tetrahedron Lett. 1986; 27: 977
• 22f Benmaarouf-Khallaayoun Z. Baboulene M. Speziale V. Lattes A. J. Organomet. Chem. 1986; 306: 283
• 22g Wang KK. Dhumrongvaraporn S. Tetrahedron Lett. 1987; 28: 1007
• 22h Ichikawa J. Sonoda T. Kobayashi H. Tetrahedron Lett. 1989; 30: 6379
• 22i Hoshi M. Masuda Y. Arase A. J. Chem. Soc., Perkin Trans. 1 1990; 12: 3237
• 22j Brown HC. Iyer RR. Mahindroo VK. Bhat NG. Tetrahedron: Asymmetry 1991; 2: 277
• 22k Brown HC. Mandal AK. J. Org. Chem. 1992; 57: 4970
• 22l Periasamy M. Bhanu Prasad A. Suseela Y. Tetrahedron 1995; 51: 2743
• 22m Yang DY. Huang X. J. Organomet. Chem. 1996; 523: 139
• 22n Hoshi M. Tanaka H. Shirakawa K. Arase A. Chem. Commun. 1999; 627
• 22o Smith K. Balakit AA. El-Hiti GA. Tetrahedron 2012; 68: 7834
• 23 Dutheuil G. Webster MP. Worthington PA. Aggarwal VK. Angew. Chem. Int. Ed. 2009; 48: 6317
• 24 Pulis AP. Blair DJ. Torres E. Aggarwal VK. J. Am. Chem. Soc. 2013; 135: 16054
• 25a Sonawane RP. Jheengut V. Rabalakos C. Larouche-Gauthier R. Scott HK. Aggarwal VK. Angew. Chem. Int. Ed. 2011; 50: 3760
• 25b Shimizu M. Angew. Chem. Int. Ed. 2011; 50: 5998
• 26 Blair DJ. Tanini D. Bateman JM. Scott HK. Myers EL. Aggarwal VK. Chem. Sci. 2017; 8: 2898
• 27 Linstrumelle G. Alami M. Vinylmagnesium Bromide. In e-EROS Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons; Chichester: 2001
• 28 Armstrong RJ. Niwetmarin W. Aggarwal VK. Org. Lett. 2017; 19: 2762

For related use of DMSO to promote boronate complex formation with vinyl Grignard reagents, see:
• 29a Lovinger GJ. Aparece MD. Morken JP. J. Am. Chem. Soc. 2017; 139: 3153
• 29b Edelstein EK. Namirembe S. Morken JP. J. Am. Chem. Soc. 2017; 139: 5027
• 30 For a related example involving trialkylboranes, see: Levy AB. Schwartz SJ. Wilson N. Christie B. J. Organomet. Chem. 1978; 156: 123
• 31 Wang Y. Noble A. Myers EL. Aggarwal VK. Angew. Chem. Int. Ed. 2016; 55: 4270
• 32 Blair DJ. Fletcher CJ. Wheelhouse KM. P. Aggarwal VK. Angew. Chem. Int. Ed. 2014; 53: 5552
• 33a Aggarwal VK. Binanzer M. de Ceglie MC. Gallanti M. Glasspoole BW. Kendrick SJ. F. Sonawane RP. Vázquez-Romero A. Webster MP. Org. Lett. 2011; 13: 1490

For related examples see:
• 33b Bhat NG. Lai WC. Carroll MB. Tetrahedron Lett. 2007; 48: 4267
• 33c Meng F. Jang H. Hoveyda AH. Chem. Eur. J. 2013; 19: 3204
• 34 Armstrong RJ. García-Ruiz C. Myers EL. Aggarwal VK. Angew. Chem. Int. Ed. 2017; 56: 786
• 35 Armstrong RJ. Sandford C. García-Ruiz C. Aggarwal VK. Chem. Commun. 2017; 53: 4922

For other examples of Zweifel olefination in synthesis, see:
• 36a Man H.-W. Hiscox WC. Matteson DS. Org. Lett. 1999; 1: 379
• 36b Fletcher CJ. Blair DJ. Wheelhouse KM. P. Aggarwal VK. Tetrahedron 2012; 68: 7598
• 36c Shoba VM. Thacker NC. Bochat AJ. Takacs JM. Angew. Chem. Int. Ed. 2016; 55: 1465
• 36d Casoni G. Myers EL. Aggarwal VK. Synthesis 2016; 48: 3241
• 36e Chakrabarty S. Takacs JM. J. Am. Chem. Soc. 2017; 139: 6066
• 37 Varela A. Garve LK. B. Leonori D. Aggarwal VK. Angew. Chem. Int. Ed. 2017; 56: 2127
• 38 Kleinnijenhuis RA. Timmer BJ. J. Lutteke G. Smits JM. M. de Gelder R. van Maarseveen JH. Hiemstra H. Chem. Eur. J. 2016; 22: 1266
• 39 Blaisdell TP. Morken JP. J. Am. Chem. Soc. 2015; 137: 8712
• 40 Noble A. Roesner S. Aggarwal VK. Angew. Chem. Int. Ed. 2016; 55: 15920
• 41 Mercer JA. M. Cohen CM. Shuken SR. Wagner AM. Smith MW. Moss FR. Smith MD. Vahala R. Gonzalez-Martinez A. Boxer SG. Burns NZ. J. Am. Chem. Soc. 2016; 138: 15845
• 42 Xu S. Lee C.-T. Rao H. Negishi E. Adv. Synth. Catal. 2011; 353: 2981
• 43 Meng F. McGrath KP. Hoveyda AH. Nature 2014; 513: 367