Chloramine Salt Mediated Oxidative Halogenation of Terminal Alkynes with KI or NaBr: Practical Synthesis of 1-Bromoalkynes and 1-Iodoalkynes

Abstract

A direct oxidative halogenation of terminal alkynes has been realized using chloramine-B as the oxidant and KI or NaBr as the halogen source. This reaction enables a general and practical access to synthetically valuable 1-bromoalkynes and 1-iodoalkynes in good to excellent yields under mild reaction conditions.

Key words

oxidative halogenation - 1-bromoalkynes - 1-iodoalkynes - chloramine salt - terminal alkynes

• References and Notes

• 1a Brand JP. Waser J. Chem. Soc. Rev. 2012; 41: 4165
• 1b Wu W. Jiang H. Acc. Chem. Res. 2014; 47: 2483
• 1c Shi W. Lei A. Tetrahedron Lett. 2014; 55: 2763
• 1d Shi W. Curr. Organocatal. 2015; 2: 2

For selected examples, see:
• 2a Naskar D. Roy S. J. Org. Chem. 1999; 64: 6896
• 2b Wang Z. Campagna S. Yang K. Xu G. Pierce ME. Fortunak JM. Confalone PN. J. Org. Chem. 2000; 65: 1889
• 2c Das JP. Roy S. J. Org. Chem. 2002; 67: 7861
• 2d Pelletier G. Lie S. Mousseau JJ. Charette AB. Org. Lett. 2012; 14: 5464
• 2e Starkov P. Rota F. D’Oyley JM. Sheppard TD. Adv. Synth. Catal. 2012; 354: 3217
• 2f Gulia N. Pigulski B. Charewicz M. Szafert S. Chem. Eur. J. 2014; 20: 2746
• 3a Rao ML. N. Periasamy M. Synth. Commun. 1995; 25: 2295
• 3b Chowdhury RM. Wilden JD. Org. Biomol. Chem. 2015; 13: 5859
• 3c Wilkins LC. Lawson JR. Wieneke P. Rominger F. Hashmi AS. K. Hansmann MM. Melen RL. Chem. Eur. J. 2016; 22: 14618
• 3d Nouzarian M. Hosseinzadeh R. Golchoubian H. Synth. Commun. 2013; 43: 2913
• 3e Gómez-Herrera A. Nahra F. Brill M. Nolan SP. Cazin CS. J. ChemCatChem 2016; 8: 3381
• 3f Yan J. Li JH. Cheng DP. Synlett 2007; 2442
• 3g Nosel P. Lauterbach T. Rudolph M. Rominger F. Hashmi AS. K. Chem. Eur. J. 2013; 19: 8634
• 3h Chen SN. Lin TC. Hung TT. Tsai FY. J. Chin. Chem. Soc. 2009; 56: 1078
• 3i Nishiguchi I. Kanbe O. Itoh K. Maekawa H. Synlett 2000; 89
• 3j Mader S. Molinari L. Rudolph M. Rominger F. Hashmi AS. K. Chem. Eur. J. 2015; 21: 3910
• 3k Hashmi AS. K. Dopp R. Lothschutz C. Rudolph M. Riedel D. Rominger F. Adv. Synth. Catal. 2010; 352: 1307
• 3l Liu Y. Huang D. Huang J. Maruoka K. J. Org. Chem. 2017; 82: 11865
• 3m Rao DS. Reddy TR. Kashyap S. Org. Biomol. Chem. 2018; 16: 1508
• 3n Chen WW. Zhang JL. Wang B. Zhao ZX. Wang XY. Hu YF. J. Org. Chem. 2015; 80: 2413
• 3o Naskar D. Roy S. J. Org. Chem. 1999; 64: 6896
• 3p Wang B. Zhang JL. Wang XY. Liu N. Chen WW. Hu YF. J. Org. Chem. 2013; 78: 10519
• 3q Reddy KR. Venkateshwar M. Maheswari CU. Kumar PS. Tetrahedron Lett. 2010; 51: 2170
• 3r Meng L.-G. Cai P.-J. Guo Q.-X. Xue S. Synth. Commun. 2008; 38: 225
• 3s Brunel Y. Rousseau G. Tetrahedron Lett. 1995; 36: 2619
• 3t Casarlni A. Dembech P. Reginato G. Ricci A. Seconi G. Tetrahedron Lett. 1991; 32: 2169
• 4a Villeneuve K. Riddell N. Jordan RW. Tsui G. Tam W. Angew. Chem. Int. Ed. 2004; 43: 610
• 4b Leyva-Pérez A. Rubio-Marqués P. Al-Deyab SS. AlResayes SI. Corma A. ACS Catal. 2011; 1: 601
• 4c Li Y. Liu X. Ma D. Liu B. Jiang H. Adv. Synth. Catal. 2012; 354: 2683
• 4d Reddy MS. Kumar YK. Thirupathi N. Org. Lett. 2012; 14: 824
• 4e Corey EJ. Ravindranathan T. J. Am. Chem. Soc. 1972; 94: 4013
• 4f Werboom W. Westmijze H. Notten LJ. Vermeer P. Bos HJ. T. Synthesis 1979; 296
• 4g Eglington G. McCrae W. J. Chem. Soc. 1963; 2295
• 4h Kloster-Jensen E. Tetrahedron 1966; 22: 965
• 4i Hori Y. Nagano Y. Uchiyama H. Yamada Y. Taniguchi H. Chem. Lett. 1978; 73
• 4j Abele E. Rubina K. Abele R. Gaukhman A. Lukevics A. J. Chem. Res., Synop. 1998; 618
• 4k Wagner A. Heitz MP. Mioskowski C. Tetrahedron Lett. 1990; 31: 3141
• 4l Rajbongshi KK. Hazarika D. Phukan P. Tetrahedron 2016; 72: 4151
• 5 Li MR. Li YJ. Zhao BZ. Liang FS. Jin LY. RSC Adv. 2014; 4: 30046
• 6 Shi W. Guan Z. Cai P. Chen H. J. Catal. 2017; 353: 199
• 7a Campbell MM. Johnson G. Chem. Rev. 1978; 78: 65
• 7b Agnihotri G. Synlett 2005; 2857
• 7c Kolvari E. Choghamarani AG. Salehi P. Shirini F. Zolfigol MA. J. Iran. Chem. Soc. 2007; 4: 126
• 7d Minakata S. Acc. Chem. Res. 2009; 42: 1172
• 8a Liu X. Hu Q. Yuan Z. Liu P. Org. Biomol. Chem. 2014; 12: 7494
• 8b Liu P. Guo J. Wei W. Liu X. Sun P. Eur. J. Org. Chem. 2016; 2105
• 8c Guo J. Chen S. Liu J. Guo J. Chen W. Cai Q. Liu P. Sun P. Eur. J. Org. Chem. 2017; 4773
• 8d Liu X. Zhou Y. Yang Z. Li Q. Zhao L. Liu P. J. Org. Chem. 2018; 83: 4665
• 9a Minakata S. Hayakawa J. Chem. Commun. 2011; 47: 1905
• 9b Ganesh V. Sureshkumar D. Chandrasekaran S. Angew. Chem. 2011; 123: 6000
• 9c Zhu Y.-Z. Zhang X.-Q. Liu F. Gu H.-M. Zhu H. Synth. Commun. 2013; 43: 2943
• 9d Kiyokawa K. Kojima T. Hishikawa Y. Minakata S. Chem. Eur. J. 2015; 21: 15548
• 10 General Procedure for the Synthesis of 1-Iodoalkynes A 25 mL round-bottom flask with a magneton was charged with terminal alkyne 1 (0.5 mmol), KI (99 mg, 1.2 equiv), and MeCN (3 mL) under air at room temperature, and then chloramine-B (160 mg, 1.5 equiv) was added. The mixture was stirred for 2 h. After that, the reaction mixture was filtered. The filtrate was concentrated under reduced pressure. Purification of the residue by flash column chromatography on silica gel using petroleum ether/ethyl acetate as eluent afforded the desired product 2.
• 11 General Procedure for the Synthesis of 1-Bromoalkynes A 25 mL round-bottom flask with a magneton was charged with terminal alkyne 1 (0.5 mmol), NaBr (77 mg, 1.5 equiv), and MeCN/H₂O (3:1, 4 mL,) under air at room temperature, and then chloramine-B (320 mg, 3.0 equiv) was added. The mixture was stirred at 70 °C for 24 h. After that, the reaction mixture was cooled to room temperature and then filtered. The filtrate was concentrated under reduced pressure. Purification of the residue by flash column chromatography on silica gel using petroleum ether/ethyl acetate as eluent afforded the desired product 3.