Vicinal Dichlorination of Olefins Using NH₄Cl and Oxone^®

Abstract

A mild and efficient protocol for the preparation of 1,2-dichloroalkane derivatives from olefins using NH₄Cl and Oxone^® at room temperature is described. A variety of terminal, internal, and cyclic alkenes reacted smoothly to give the corresponding dichlorinated products in good to excellent yields. Moreover, 1,2-disubstituted symmetrical and unsymmetrical olefins dichlorinated with moderate to excellent diastereoselectivity. This method precludes the use of acidic additives and transition metals in the synthesis of vicinal dichlorides.

Key words

vicinal dichlorination - olefins - NH₄Cl - Oxone^® - diastereoselectivity

• References

• 1a Jana R, Pathak TP, Sigman MS. Chem. Rev. 2011; 111: 1417
• 1b Krief A, Laval A.-M. Chem. Rev. 1999; 99: 745
• 2a Fauvarque J. Pure Appl. Chem. 1996; 68: 1713
• 2b Rossberg M, Lendle W, Pfleiderer G, Tögel A, Dreher E.-L, Langer E, Rassaerts H, Kleinschmidt P, Strack H, Cook R, Beck U, Lipper K.-A, Torkelson TR, Löser E, Beutel KK, Mann T. Chlorinated Hydrocarbons . In Ullmann’s Encyclopedia of Industrial Chemistry (electronic edition) . Wiley-VCH; Weinheim: 2006: DOI: 10.1002/14356007.a06_233.pub2
• 2c Dagani MJ, Barda HJ, Benya TJ, Sanders DC. Bromine Compounds . In Ullmann’s Encyclopedia of Industrial Chemistry (electronic edition) . Wiley-VCH; Weinheim: 2002: DOI: 10.1002/14356007.a04_405
• 3a Gribble GW. Prog. Chem. Org. Nat. Prod. 2010; 91: 1
• 3b Gribble GW. Prog. Chem. Org. Nat. Prod. 1996; 68: 1; and references cited therein
• 4 Gribble GW. J. Chem. Educ. 2004; 81: 1441
• 5a Metrangolo P, Resnati G. Science 2008; 321: 918
• 5b Naumann K. J. Prakt. Chem. 1999; 341: 417

For pioneering studies on this class of molecules, see:
• 6a Elovson J, Vagelos PR. Proc. Natl. Acad. Sci. U.S.A. 1969; 62: 957
• 6b Elovson J, Vagelos PR. Biochemistry 1970; 9: 3110
• 6c Haines TH. Annu. Rev. Microbiol. 1973; 27: 403
• 6d Hansen JA. Physiol. Plant. 1973; 29: 234
• 6e Mercer EI, Davies CL. Phytochemistry 1974; 13: 1607
• 6f Mercer EI, Davies CL. Phytochemistry 1975; 14: 1545
• 6g Mercer EI, Davies CL. Phytochemistry 1979; 18: 457
• 7a Kawahara T, Okino T. Stud. Nat. Prod. Chem. 2012; 219
• 7b Nilewski C, Carreira EM. Eur. J. Org. Chem. 2012; 1685
• 7c Bedke DK, Vanderwal CD. Nat. Prod. Rep. 2011; 28: 15
• 7d Umezawa T, Matsuda F. J. Synth. Org. Chem. Jpn. 2011; 69: 1122
• 8a Shibuya GM, Kanady JS, Vanderwal CD. J. Am. Chem. Soc. 2008; 130: 12514
• 8b Nilewski C, Geisser RW, Carreira EM. Nature 2009; 457: 573
• 8c Kanady JS, Nguyen JD, Ziller JW, Vanderwal CD. J. Org. Chem. 2009; 74: 2175
• 8d Nilewski C, Geisser RW, Ebert M.-O, Carreira EM. J. Am. Chem. Soc. 2009; 131: 15866
• 8e Bedke DK, Shibuya GM, Pereira A, Gerwick WH, Haines TH, Vanderwal CD. J. Am. Chem. Soc. 2009; 131: 7570
• 9a Donnelly KD, Fristad WE, Gellerman BJ, Peterson JR, Selle BJ. Tetrahedron Lett. 1984; 25: 607
• 9b Morella AM, Ward AD. Tetrahedron Lett. 1984; 25: 1197
• 9c Yakabe S, Hirano M, Morimoto T. Synth. Commun. 1998; 28: 1871
• 9d Markó IE, Richardson PR. Tetrahedron Lett. 1991; 32: 1831
• 9e Barhate NB, Gajare AS, Wakharkar RD, Bedekar AV. Tetrahedron 1999; 55: 11127
• 9f He Y, Goldsmith CR. Synlett 2010; 1377
• 9g Kitamura T, Tazawa Y, Morshed MH, Kobayashi S. Synthesis 2012; 44: 1159
• 10a Richardson PR, Markó IE. Synlett 1991; 733
• 10b Markó IE, Richardson PR, Bailey M, Magure AR, Coughlan N. Tetrahedron Lett. 1997; 38: 2339
• 10c Hazra BG, Chordia MD, Basu S, Bahule BB, Pore VS, Naskar D. J. Chem. Res., Synop. 1998; 8
• 11 Schlama T, Gabriel K, Gouverneur V, Mioskowski C. Angew. Chem., Int. Ed. Engl. 1997; 36: 2342
• 12a Kamada Y, Kitamura Y, Tanaka T, Yoshimistu T. Org. Biomol. Chem. 2013; 11: 1598
• 12b Ren J, Tong R. Org. Biomol. Chem. 2013; 11: 4312
• 13a Krishna Mohan KV. V, Narender N.. Synthesis 2012; 44: 15
• 13b Narender N, Krishna Mohan KV. V, Srinivasu P, Kulkarni SJ, Raghavan KV. Indian J. Chem., Sect. B 2004; 43: 1335
• 13c Swamy P, Kumar MA, Reddy MM, Narender N. Chem. Lett. 2012; 41: 432
• 13d Reddy MM, Kumar MA, Swamy P, Narender N. Tetrahedron Lett. 2011; 52: 6554
• 13e Kumar MA, Rohitha CN, Reddy MM, Swamy P, Narender N. Tetrahedron Lett. 2012; 53: 191
• 13f Kumar MA, Rohitha CN, Narender N. Tetrahedron Lett. 2012; 53: 1401
• 13g Naresh M, Kumar MA, Reddy MM, Swamy P, Nanubolu JB, Narender N. Synthesis 2013; 45: 1497
• 14 Hussain H, Green IR, Ahmed I. Chem. Rev. 2013; 113: 3329
• 15 Kovacic P, Field KW. J. Org. Chem. 1971; 36: 3566
• 16 Denton RM, Tang X, Przeslak A. Org. Lett. 2010; 12: 4678
• 17 Nicolaou KC, Simmons NL, Ying Y, Heretsch PM, Chen JS. J. Am. Chem. Soc. 2011; 133: 8134
• 18 Negoro T, Ikeda Y. Bull. Chem. Soc. Jpn. 1984; 57: 2116
• 19 Snyder SA, Treitler DS, Brucks AP. J. Am. Chem. Soc. 2010; 132: 14303
• 20 Hernandez-Torres G, Tan B, Barbas CF. Org. Lett. 2012; 14: 1858
• 21 Han J, Wang Q, Chang X, Liu Y, Wang Y, Meng J. Tetrahedron 2011; 67: 8865