Dichlorination of α-Diazo-β-dicarbonyls Using (Dichloroiodo)benzene

Keith E. Coffey; Graham K. Murphy

doi:10.1055/s-0034-1380304

Synlett, Table of Contents

Synlett 2015; 26(08): 1003-1007
DOI: 10.1055/s-0034-1380304

synpacts

Dichlorination of α-Diazo-β-dicarbonyls Using (Dichloroiodo)benzene

Keith E. Coffey

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L 3G1, Canada Email: graham.murphy@uwaterloo.ca

,

Graham K. Murphy*

Department of Chemistry, University of Waterloo, 200 University Ave W., Waterloo, ON, N2L 3G1, Canada Email: graham.murphy@uwaterloo.ca

› Author Affiliations

Abstract

All articles of this category

Abstract

α-Diazo-β-dicarbonyl compounds were chlorinated using (dichloro)iodobenzene and an activating catalyst. A broad range of reaction rates was observed, which paralleled the relative stability/nucleophilicity of the diazo compounds. Acyclic diazocarbonyls reacted faster than cyclics, and β-diketones were much faster to react than β-keto esters or β-diesters. Lewis acid activation was used for the first time, allowing us to overcome instances of poor chemoselectivity. Though the yields ranged from low to good, this chlorination reaction has again proven a mild and effective halogenation strategy.

Key words

diazo compounds - hypervalent iodine - halogenation - catalysis - ylides

Full Text

References

References and Notes
1 Willgerodt O. J. Prakt. Chem. 1886; 33: 6

2a Stang PJ, Zhdankin VV. Chem. Rev. 1996; 96: 1123
2b Zhdankin VV, Stang PJ. Chem. Rev. 2002; 102: 2523
2c Zhdankin VV, Stang PJ. Chem. Rev. 2008; 108: 5299
2d Zhdankin VV. ARKIVOC 2009; (i): 1
2e Zhdankin VV. Hypervalent Iodine Chemistry: Preparation, Structure, and Synthetic Applications of Polyvalent Iodine Compounds. Wiley; Chichester: 2013: 468

3 Moriarty RM, Kosmeder JW, Zhdankin VV, Courillon C, Lacôte E, Malacria M, Darses B, Dauban P. Iodosylbenzene. In e-EROS Encyclopedia of Reagents for Organic Synthesis [Online]. Wiley; New York: 2012. DOI: 10.1002/047084289X.ri039.pub4
4 Koser GF, Ollevier T, Desyroy V. [Hydroxy(tosyloxy)iodo]-benzene. In e-EROS Encyclopedia of Reagents for Organic Synthesis [Online]. Wiley; New York: 2004. DOI: 10.1002/047084289X.rh070.pub2

5a Eisenberger P, Gischig S, Togni A. Chem. Eur. J. 2006; 12: 2579
5b Kieltsch I, Eisenberger P, Togni A. Angew. Chem. Int. Ed. 2007; 46: 754

6 Moriarty RM, Chany CJ, Kosmeder JW. (Diacetoxyiodo)benzene. In e-EROS Encyclopedia of Reagents for Organic Synthesis [Online]. Wiley; New York: 2005. DOI: 10.1002/047084289X.rd005m.pub2

7a Merritt EA, Olofsson B. Synthesis 2011; 517
7b Dong DQ, Hao SH, Wang ZL, Chen C. Org. Biomol. Chem. 2014; 12: 4278

8a Moriarty RM, Prakash I, Prakash O, Freeman WA. J. Am. Chem. Soc. 1984; 106: 6082
8b Huang ZZ, Yu XC, Huang X. Tetrahedron Lett. 2002; 43: 6823
8c Matveeva ED, Podrugina TA, Grishin YK, Tkachev VV, Zhdankin VV, Aldoshin SM, Zefirov NS. Russ. J. Org. Chem. 2003; 39: 536
8d Zhdankin VV, Maydanovych O, Herschbach J, Bruno J, Matveeva ED, Zefirov NS. J. Org. Chem. 2003; 68: 1018

9 Roedig A, Aman H, Fahr E. Liebigs Ann. Chem. 1964; 675: 47
10 Tao J, Tran R, Murphy GK. J. Am. Chem. Soc. 2013; 135: 16312

11a Murphy GK, Abbas FZ, Poulton AV. Adv. Synth. Catal. 2014; 356: 2919
11b Coffey KE, Moreira R, Abbas FZ, Murphy GK. Org. Biomol. Chem. 2015; 13: 682

12 Zanka A, Takeuchi H, Kubota A. Org. Process Res. Dev. 1998; 2: 270

13a Kim JJ, Kweon DH, Cho SD, Kim HK, Lee SG, Yoon YJ. Synlett 2006; 194
13b Mei Y, Bentley PA, Du J. Tetrahedron Lett. 2008; 49: 3802
13c Wang J, Li H, Zhang D, Huang P, Wang Z, Zhang R, Liang Y, Dong D. Eur. J. Org. Chem. 2013; 5376

For an example using PhICl₂, see:

13d Duan X, Zhou H, Tian X, Liu J, Ma J. Synthesis 2015; 47: 777

14 Patrick TB, Scheibel JJ, Cantrell GL. J. Org. Chem. 1981; 46: 3917
15 Lee KI, Youn JI, Shim YK, Kim WJ. Bull. Korean Chem. Soc. 1992; 13: 226
16 Olah GA, Welch J. Synthesis 1974; 896
17 Yusubov MS, Zhdankin VV. Curr. Org. Synth. 2012; 9: 247

18a Sket B, Zupan M, Zupet P. Tetrahedron 1984; 40: 1603
18b Chen JM, Zeng XM, Middleton K, Zhdankin VV. Tetrahedron Lett. 2011; 52: 1952

19 Yusubov MS, Drygunova LA, Zhdankin VV. Synthesis 2004; 2289
20 Thorat PB, Bhong BY, Karade NN. Synlett 2013; 24: 2061
21 Podgorsek A, Jurisch M, Stavber S, Zupan M, Iskra J, Gladysz JA. J. Org. Chem. 2009; 74: 3133
22 Kitamura T, Tazawa Y, Morshed MH, Kobayashi S. Synthesis 2012; 44: 1159

23a Richardson RD, Wirth T. Angew. Chem. Int. Ed. 2006; 45: 4402
23b Ochiai M, Miyamoto K. Eur. J. Org. Chem. 2008; 4229
23c Dohi T, Kita Y. Chem. Commun. 2009; 2073

24 Caution: Diazo compounds are reported to be toxic and potentially explosive. Appropriate safety measures should be observed when working with them.

25a Regitz M, Maas G. Diazo Compounds: Properties and Synthesis . Academic Press; Orlando: 1986. xi
25b Doyle MP, Mckervey MA, Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds : From Cyclopropanes to Ylides. Wiley; New York: 1998: 652

26 Bug T, Hartnagel M, Schlierf C, Mayr H. Chem. Eur. J. 2003; 9: 4068
27 Abel EW, Stone FG. A, Wilkinson G. Comprehensive Organometallic Chemistry II: A Review of the Literature 1982–1994 . Pergamon Press; Oxford: 1995. 1st ed.

In carbenoid reactions, elevated temperatures are required for diazo Meldrum’s acid to react. See:

28a Somai Magar KB, Lee YR, Kim SH. Tetrahedron 2013; 69: 9294
28b Shi J, Yan Y, Li Q, Xu HE, Yi W. Chem. Commun. 2014; 50: 6483

29 For example, chlorination of 23d using 5 mol% DMAP or 2,6-lutidine, or either 1 mol% or 10 mol% pyridine gave mixtures of 24d/25d. The best improvement came from using 5 mol% pyridine in DCE, which gave 24d in 51% yield. However, chlorinating 23a in DCE gave 24a in only 43% yield, so this effect was not pursued.
30 Using DCE in the AlCl₃-catalyzed reactions gave lower yields than CH₂Cl₂: 24b, 8%; 24d, 49%.
31 Another dramatic Lewis acid effect was found when chlorinating 10-diazoanthrone. In contrast to pyridine, which gave anthroquinone as the product, using AlCl₃ gave 10,10-dichloroanthrone as the sole product.
32 Zhao XF, Zhang C. Synthesis 2007; 551

Supplementary Material

Supporting Information