Sulfur Betaines from S-Propargyl Xanthates. Unusual Chemistry from a Simple Functional Group

Published as part of the 50 Years SYNTHESIS – Golden Anniversary Issue

This paper is dedicated with respect and affection to Professor Nguyen Trong Anh (Ecole Polytechnique).

Abstract

S-Propargyl xanthates undergo upon heating a [3,3] sigmatropic rearrangement followed by a reversible ring closure into a novel betaine. This betaine can be implicated in carbon–carbon bond forming processes, in the synthesis of esters, in the inversion of secondary alcohols, in the formation of alkenes, for the generation of rigid, cisoid dienes that are highly reactive in both inter- and intra-molecular Diels–Alder cycloadditions, and in various other synthetically useful transformations.

1 Introduction

2 An Unexpected Transformation

3 Evidence for the Betaine Intermediate

4 A Method for the Synthesis of Esters and for the Inversion of Secondary Alcohols

5 A General Alkylation Process

6 The Case of Carbon Acids

7 A Synthesis of Alkenes

8 Further Trapping Experiments. Concerted or Not Concerted?

9 Rigid Cisoid Dienes

10 Propargyl Radicals

11 Concluding Remarks

Key words

S-propargyl xanthates - sigmatropic rearrangement - betaines - esters - inversion - cycloaddition

• References


For recent reviews, see:
• 1a Quiclet-Sire B, Zard SZ. Isr. J. Chem. 2017; 57: 202
• 1b Quiclet-Sire B, Zard SZ. Pure Appl. Chem. 2011; 83: 519
• 1c Quiclet-Sire B, Zard SZ. Top Curr. Chem. 2006; 264: 201
• 1d Quiclet-Sire B, Zard SZ. Chem. Eur. J. 2006; 12: 6002

For a detailed mechanistic discussion, see:
• 1e Zard SZ. J. Phys. Org. Chem. 2012; 25: 953

For an account of the discovery of this process, see:
• 1f Zard SZ. Aust. J. Chem. 2006; 59: 663
• 2 Handbook of RAFT Polymerization . Barner-Kowollik C. Wiley-VCH; Weinheim: 2008
• 3 Perrier S. Macromolecules 2017; 50: 7433
• 4 Boivin J, Tailhan C, Zard SZ. J. Am. Chem. Soc. 1991; 113: 5874
• 5 Alabugin IV, Timokhin VI, Abrams JN, Manoharan M, Abrams R, Ghiviriga I. J. Am. Chem. Soc. 2008; 130: 10984 ; and references cited therein
• 6a Giese B. Angew. Chem., Int. Ed. Engl. 1985; 24: 553
• 6b Giese B, Kretzschmar G. Chem. Ber. 1984; 117: 3175
• 6c Giese B, Meixner J. Tetrahedron Lett. 1977; 2779
• 6d Giese B, Meixner J. Tetrahedron Lett. 1977; 2183
• 7a Hudlicky T, Reed JW. Angew. Chem. Int. Ed. 2010; 49: 4864
• 7b Goldschmidt Z, Crammer B. Chem. Soc. Rev. 1988; 17: 229
• 7c Mil’vitskaya EM, Tarakanova AV, Plate AF. Russ. Chem. Rev. 1976; 45: 469
• 8 Haley NF, Fichtner MW. J. Org. Chem. 1980; 45: 2959
• 9 Boivin J, Henriet E, Tailhan C, Zard SZ. Tetrahedron Lett. 1993; 34: 2763
• 10 Bendikov M, Wudl F, Perepichka DF. Chem. Rev. 2004; 104: 4891
• 11 Boivin J, Henriet EB, Zard SZ. J. Am. Chem. Soc. 1994; 116: 9739
• 12 Fauré-Tromeur M, Zard SZ. Tetrahedron Lett. 1998; 39: 7301
• 13 Fauré-Tromeur M. Ph D. Thesis . Université Pierre et Marie Curie; Paris: 1999
• 14 Corey EJ, Raju N. Tetrahedron Lett. 1983; 24: 5571
• 15 Henriet EB. Ph.D. Thesis 1995
• 16 Schwartz BD, White LV, Banwell MG, Willis AC. J. Org. Chem. 2011; 76: 8560
• 17 Clemente-Tejeda D, Ortiz-Lara J.-C, Zard SZ. Synthesis 2016; 48: 3393
• 18 For a review of alkylation processes, see: Lamoureux G, Agüero C. ARKIVOC 2009; (i): 251
• 19 Remy R, Bochet CG. Eur. J. Org. Chem. 2018; 316
• 20a Vogensen SB, Frydenvang K, Greenwood JR, Postorino G, Nielsen B, Pickering DS, Ebert B, Bølcho U, Egebjerg J, Gajhede M, Kastrup JS, Johansen TN, Clausen RP, Krogsgaard-Larsen P. J. Med. Chem. 2007; 50: 2408
• 20b Vogensen SB, Clausen RP, Greenwood JR, Johansen TN, Pickering DS, Nielsen B, Ebert B, Bølcho U, Krogsgaard-Larsen P. J. Med. Chem. 2005; 48: 3438

For a review on the alkylation of tetrazoles, see:
• 20c Ostrovskii VA, Koren AO. Heterocycles 2000; 53: 1421
• 21 Wenger J, Niderman T, Mathews C. In Modern Crop Protection Compounds. Volume 1: Herbicides . Krämer W, Schirmer U, Jeschke P, Witschel M. Wiley-VCH; Weinheim: 2012: 447-478
• 22 Boivin J, Henriet EB, Zard SZ. Tetrahedron Lett. 1995; 36: 5171
• 23 Bührer M, Le Cotonnec J.-Y, Wermeille M, Bircher J. Eur. J. Clin. Pharmacol. 1986; 30: 407
• 24 Tromeur-Fauré M, Zard SZ. Tetrahedron Lett. 1999; 40: 1305
• 25 Upadhyay SK, Creech CC, Bowdy KL, Stevens ED, Jursic BS, Neumann DM. Bioorg. Med. Chem. Lett. 2011; 21: 2826
• 26 Poelert MA, Zard SZ. Synlett 1995; 325
• 27 For a review, see: Basavaiah D, Jaganmohan RaoA, Satyanarayana T. Chem. Rev. 2003; 103: 811
• 28 Poelert M, Roger W, Zard SZ. Chem. Commun. 1996; 743
• 29 Boivin J, Tailhan C, Zard SZ. Tetrahedron Lett. 1992; 33: 7853
• 30 Gagosz F.; Zard S. Z. Unpublished observations.
• 31a Boulle C, Cariou M, Bainville M, Gorgues A, Hudhomme P, Orduna CJ, Garín J. Tetrahedron Lett. 1997; 38: 81
• 31b Boulle C, Desmars O, Gautier N, Hudhomme P, Cariou M, Gorgues A. Chem. Commun. 1998; 2197
• 31c Hudhomme P, Boulle C, Rabreau JM, Cariou M, Jubault M, Gorgues A. Synth. Met. 1998; 94: 73
• 31d Boulle C, Gautier N, Desmars O, Hudhomme P, Cariou M, Leriche P, Khodorkovsky V, Orduna CJ, Garín J, Jubault M, Gorgues A. Synth. Met. 1999; 102: 1634
• 31e Kreher D, Cariou M, Liu S.-G, Levillain E, Veciana J, Rovira C, Gorgues A, Hudhomme P. J. Mater. Chem. 2002; 12: 2137
• 32 Harrington R, Wright D, Zard SZ. Heterocycles 2012; 86: 965
• 33 Denieul M.-P, Quiclet-Sire B, Zard SZ. Tetrahedron Lett. 1996; 37: 5495
• 34 Alameda-Angulo C, Quiclet-Sire B, Zard SZ. Tetrahedron Lett. 2006; 47: 913
• 35 For a review on transannular reactions, see: Reyes E, Uria U, Carrillo L, Vicario JL. Tetrahedron 2014; 70: 9461