A Sulfoxide Reagent for Sulfinylative Cross-Coupling

Abstract

I recently documented the strategic use of a sulfoxide reagent as a sulfur monoxide equivalent to enable one-pot, three-component syntheses of sulfoxides and sulfinamides. The sulfoxide reagent donates the SO unit upon the reaction with Grignard reagents (RMgX) as sulfenate anions (RSO^–). The anionic sulfur intermediates can be readily transformed into sulfoxides and sulfinamides via trapping with appropriate carbon and nitrogen electrophiles. This Synpacts article highlights my first efforts to establish a general sulfinylative cross-coupling platform.

1 Introduction

2 Development of a Sulfoxide Reagent as a Sulfur Monoxide Equivalent

3 Conclusions and Future Directions

Key words

sulfinylative cross-coupling - Grignard reagents - one-pot synthesis - sulfinamides - sulfoxides

Publication History

Received: 09 April 2023

Accepted after revision: 25 April 2023

Accepted Manuscript online:
25 April 2023

Article published online:
25 May 2023

• References

• 1a Taniguchi N. Eur. J. Org. Chem. 2016; 2157
• 1b Chatterjee S, Makai S, Morandi B. Angew. Chem. Int. Ed. 2021; 60: 758
• 2a Cogan DA, Liu G, Kim K, Backes BJ, Ellman JA. J. Am. Chem. Soc. 1998; 120: 8011
• 2b Mei H, Liu J, Pajkert R, Röschenthaler G.-V, Han J. Org. Biomol. Chem. 2020; 18: 3761
• 3a Davis FA, Zhang Y, Andemichael Y, Fang T, Fanelli DL, Zhang H. J. Org. Chem. 1999; 64: 1403
• 3b Ruano JL. G, Parra A, Yuste F, Mastranzo VM. Synthesis 2008; 311
• 4a Billard T, Greiner A, Langlois BR. Tetrahedron 1999; 55: 7243
• 4b Zhu R.-H, Shi X.-X. Tetrahedron: Asymmetry 2011; 22: 387
• 5 Woolven H, González-Rodríguez C, Marco I, Thompson AL, Willis MC. Org. Lett. 2011; 13: 4876
• 6 Lenstra DC, Vedovato V, Ferrer Flegeau E, Maydom J, Willis MC. Org. Lett. 2016; 18: 2086
• 7 Lo PK. T, Oliver GA, Willis MC. J. Org. Chem. 2020; 85: 5753
• 8 Saito F. Angew. Chem. Int. Ed. 2022; 61: e202213872
• 9a Singh SP, O’Donnell JS, Schwan AL. Org. Biomol. Chem. 2010; 8: 1712
• 9b Bernoud E, Le Duc G, Bantreil X, Prestat G, Madec D, Poli G. Org. Lett. 2010; 12: 320
• 9c Jia T, Bellomo A, Montel S, Zhang M, El Baina K, Zheng B, Walsh PJ. Angew. Chem. Int. Ed. 2014; 53: 260
• 9d Gelat F, Lohier JF, Gaumont AC, Perrio S. Adv. Synth. Catal. 2015; 357: 2011
• 9e Chang M.-Y, Cheng Y.-C, Chan C.-K. Tetrahedron 2016; 72: 4068
• 10 Herron JT, Huie RE. Chem. Phys. Lett. 1980; 76: 322
• 11 Ham J, Yang I, Kang H. J. Org. Chem. 2004; 69: 3236
• 12 Dragoli DR, Burdett MT, Ellman JA. J. Am. Chem. Soc. 2001; 123: 10127
• 13 Smith K, Hou D. J. Org. Chem. 1996; 61: 1530
• 14 Oae S, Kawai T, Furukawa N. Tetrahedron Lett. 1984; 25: 69
• 15 Oae S, Uchida Y. Acc. Chem. Res. 1991; 24: 202
• 16 For a recent review on S(IV)-mediated C–C bond-forming cross-couplings, see: Perry GJ. P, Yorimitsu H. ACS Sustainable Chem. Eng. 2022; 10: 2569
• 17a Chen D.-L, Sun Y, Chen M, Li X, Zhang L, Huang X, Bai Y, Luo F, Peng B. Org. Lett. 2019; 21: 3986
• 17b Šiaučiulis M, Ahlsten N, Pulis AP, Procter DJ. Angew. Chem. Int. Ed. 2019; 58: 8779
• 17c Morofuji T, Yoshida T, Tsutsumi R, Yamanaka M, Kano N. Chem. Commun. 2020; 56: 13995
• 17d Zhou M, Tsien J, Qin T. Angew. Chem. Int. Ed. 2020; 59: 7372
• 17e Horan AM, Duong VK, McGarrigle EM. Org. Lett. 2021; 23: 9089
• 17f Ritts CB, Hoye TR. J. Am. Chem. Soc. 2021; 143: 13501
• 17g Zhou M, Tsien J, Dykstra R, Hughes JM. E, Peters BK, Merchant RR, Gutierrez O, Qin T. Nat. Chem. 2023; 15: 550
• 18 Dean WM, Šiaučiulis M, Storr TE, Lewis W, Stockman RA. Angew. Chem. Int. Ed. 2016; 55: 10013
• 19 Refvik MD, Froese RD. J, Goddard JD, Pham HH, Pippert MF, Schwan AL. J. Am. Chem. Soc. 1995; 117: 184
• 20 Sandrinelli F, Perrio S, Beslin P. J. Org. Chem. 1997; 62: 8626
• 21a Yu H, Li Z, Bolm C. Org. Lett. 2018; 20: 7104
• 21b Amos SG. E, Nicolai S, Gagnebin A, Le Vaillant F, Waser J. J. Org. Chem. 2019; 84: 3687
• 21c Wang L, Chen M, Zhang J. Org. Chem. Front. 2019; 6: 32
• 22a Caupène C, Boudou C, Perrio S, Metzner P. J. Org. Chem. 2005; 70: 2812
• 22b Maitro G, Vogel S, Sadaoui M, Prestat G, Madec D, Poli G. Org. Lett. 2007; 9: 5493
• 22c Zong L, Ban X, Kee CW, Tan C.-H. Angew. Chem. Int. Ed. 2014; 53: 11849
• 22d Jia T, Zhang M, Jiang H, Wang CY, Walsh PJ. J. Am. Chem. Soc. 2015; 137: 13887
• 22e Wang L, Chen M, Zhang P, Li W, Zhang J. J. Am. Chem. Soc. 2018; 140: 3467
• 22f Schwan AL, Michalski MM, Findlay JP. Phosphorus, Sulfur Silicon Relat. Elem. 2019; 194: 692
• 23 Dai Q, Zhang J. Adv. Synth. Catal. 2018; 360: 1123
• 24 Riddell AB, Smith MR. A, Schwan AL. J. Sulfur Chem. 2022; 43: 540
• 25 Deeming AS, Russell CJ, Willis MC. Angew. Chem. Int. Ed. 2015; 54: 1168
• 26 Under these reaction conditions, the formation of sulfinyl chlorides followed by substitution with amines (see ref. 7) is another plausible mechanism to form sulfinamides.
• 27 For an example of a recently developed sulfur monoxide surrogate, see: Joost M, Nava M, Transue WJ, Martin-Drumel M.-A, McCarthy MC, Patterson D, Cummins CC. Proc. Natl. Acad. Sci. U.S.A. 2018; 115: 5866
• 28a Ogawa S, Furukawa N. J. Org. Chem. 1991; 56: 5723
• 28b Rauhut CB, Melzig L, Knochel P. Org. Lett. 2008; 10: 3891