Citation: Xue-Ge Ling, Yan Xiong, Shu-Ting Zhang, Ruo-Feng Huang, Xiao-Hui Zhang. Effective synthesis of benzyl halides triggered by in situ prepared hypervalent halides[J]. Chinese Chemical Letters, ;2013, 24(01): 45-48. shu

Effective synthesis of benzyl halides triggered by in situ prepared hypervalent halides

1.
School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400030, China

Corresponding author: Yan Xiong,
Received Date: 29 October 2012
Available Online: 4 December 2012

An effective approach for the direct benzylhalogenation with in situ generation of hypervalent halides has been developed.A variety of benzyl halides are produced in moderate to excellent yields(up to 99%) with high regioselectivities.UV absorption spectrum is employed to detect the formation of tert-butyl hypoiodite.
- Benzyl halides,
- Bromination,
- Hypervalent,
- Iodination
1. [1]
  [1] Y.Sasson,Formation of C-Cl,C-Br and C-I bonds,in:S.Patai,Z.Rappoport(Eds.),The Chemistry of Functional Groups,Supplement D2.Part 2.The Chemistry of Halides, Pseudohalides and Azides,John Wiley&Sons,Chichester,1995,pp.535-628.
2. [2]
  [2] Selected recent examples for the iodination of sp2 C-H bond: (a)J.N.Moorthy,K.Senapati,S.Kumar,IBX-I₂ redox couple for facile generation of IOH and I⁺ :expedient protocol for iodohydroxylation of olefins and iodination of aromatics,J.Org.Chem.74(2009)6287-6290;
3. [3]
  (b)R.Badri,M.Gorjizadeh,A mild,efficient and selective iodination of aromatic compounds using iodine and 1,4-bis(triphenylphosphonium)-2-butene peroxo-disulfate,Chin.Chem.Lett.20(2009)1439-1443;
4. [4]
  (c)R.Sathiyapriya,R.Joel Karunakaran,Iodination of alkylbenzenes using ben-zyltriphenylphosphonium dichromate/I₂ system,E-J.Chem.6(2009)1164-1166;
5. [5]
  (d)O.G.Barton,J.Mattay,Iodination of activated aromatic compounds using sodium peroxodisulfate and iodine:an efficient way to iodinate alkylated calix[4] arenes,Synthesis(2008)110-114;
6. [6]
  (e)C.Y.Zhou,J.Li,S.Peddibhotla,D.Romo,Mild arming and derivatization of natural products via an In(OTf)₃-catalyzed arene iodination,Org.Lett.12(2010) 2104-2107.
7. [7]
  [3] D.D.Tanner,G.C.Gidley,Free-radical iodination.A novel synthetic method,J.Am. Chem.Soc.90(1968)808-809.
8. [8]
  [4] J.Barluenga,F.González-Bobes,J.M.González,Activation of alkanes upon reaction with PhI(OAc)₂-I₂,Angew.Chem.Int.Ed.41(2002)2556-2558.
9. [9]
  [5] (a)R.Montoro,T.Wirth,Direct iodination of alkanes,Org.Lett.5(2003)4729-4731;
10. [10]
  (b)R.Montoro,T.Wirth,Direct bromination and iodination of non-activated alkanes by hypohalite reagents,Synthesis(2005)1473-1478.
11. [11]
  [6] J.Barluenga,E.Campos-Gómez,D.Rodriguez,F.González-Bobes,J.M.González, New iodination reactions of saturated hydrocarbons,Angew.Chem.Int.Ed.44 (2005)5851-5854.
12. [12]
  [7] P.V.Chouthaiwale,G.Suryavanshi,A.Sudalai,NaIO₄-KI-NaN₃ as a new reagent system for C-H functionalization in hydrocarbons,Tetrahedron Lett.49(2008) 6401-6403.
13. [13]
  [8] (a)H.Shaw,H.D.Perlmutter,C.Gu,S.D.Arco,T.O.Quibuyen,Free-radical bromination of selected organic compounds in water,J.Org.Chem.62(1997) 236-237;
14. [14]
  (b)X.F.Jiang,M.H.Shen,Y.Tang,C.Z.Li,Chemoselective monobromination of alkanes promoted by unactivated MnO₂,Tetrahedron Lett.46(2005)487-489;
15. [15]
  (c)A.Podgorˇsek,S.Stavber,M.Zupan,J.Iskra,Association of fluorous "Phase-Vanishing" method with visible-light activation in benzylic bromination by bromine,Eur.J.Org.Chem.(2006)483-488.
16. [16]
  [9] Selected examples for benzylic bromination: (a)D.Kikuchi,S.Sakaguchi,Y.Ishii,An alternative method for the selective bromination of alkylbenzenes using NaBrO₃/NaHSO₃reagent,J.Org.Chem.63 (1998)6023-6026;
17. [17]
  (b)J.Ju,Y.J.Li,J.R.Gao,J.H.Jia,et al.,High selectively oxidative bromination of toluene derivatives by the H₂O₂-HBr system,Chin.Chem.Lett.22(2011) 382-384;
18. [18]
  (c)R.Mestres,J.Palenzuela,High atomic yield bromine-less benzylic bromina-tion,Green Chem.4(2002)314-316;
19. [19]
  (d)Y.Zhang,K.Shibatomi,H.Yamamoto,Lewis acid catalyzed highly selective halogenation of aromatic compounds,Synlett(2005)2837-2842;
20. [20]
  (e)T.A.Salama,Z.Novak,N-Halosuccinimide/SiCl₄ as general,mild and efficient systems for the a-monohalogenation of carbonyl compounds and for benzylic halogenation,Tetrahedron Lett.52(2011)4026-4029.
21. [21]
  [10] M.Akhtar,D.H.R.Barton,Reactions at position 19 in the steroid nucleus.A convenient synthesis of 19-norsteroids,J.Am.Chem.Soc.86(1964)1528-1536.
22. [22]
  [11] D.D.Tanner,G.C.Gidley,N.Das,J.E.Rowe,A.Potter,On the structure of tert-butyl hypoiodite,J.Am.Chem.Soc.106(1984)5261-5267.
23. [23]
  [12] C.Walling,A.Padwa,Positive halogen compounds.V.t-butyl hypobromite and two new techniques for hydrocarbon bromination,J.Org.Chem.27(1962) 2976-2977.
24. [24]
  [13] (a)S.Y.Zheng,Y.Xiong,J.Y.Wang,Theoretical studies on identity S_N2 reactions of lithium halide and methyl halide:A microhydration model,J.Mol.Model.16 (2010)1931-1937;
25. [25]
  (b)Y.Xiong,S.T.Zhang,X.G.Ling,X.Zhang,J.Y.Wang,Theoretical investigation on identical anionic halide-exchange S_N2 reaction processes on N-haloammonium cation NH₃X⁺ (X=F,Cl,Br,and I),Int.J.Quantum Chem.112(2012)2475-2481.
26. [26]
  [14] (a)R.Giri,J.F.Hartwig,Cu(Ⅰ)amido complexes in the ullmann reaction:reac-tions of Cu(Ⅰ)amido complexes with iodoarenes with and without autocatalysis by CuI,J.Am.Chem.Soc.132(2010)15860-15863;
27. [27]
  (b)S.Santoro,R.Z.Liao,F.Himo,Theoretical study of mechanism and selectivity of copper-catalyzed C-H bond amidation of indoles,J.Org.Chem.76(2011) 9246-9252;
28. [28]
  (c)R.T.Gephart Ⅲ,C.L.McMullin,N.G.Sapiezynski,et al.,Reaction of Cu(Ⅰ)with dialkyl peroxides:Cu(Ⅱ)-alkoxides,alkoxy radicals,and catalytic C-H etherifica-tion,J.Am.Chem.Soc.134(2012)17350-17353.
29. [29]
  [15] Salt-promoted reactions were reported by our group: (a)Y.Xiong,X.Q.Zhang,Significant heterogeneous carbonate salt catalyzed acetylation of alcohols via a transesterification process with carbonate salt-activated alcohol ¹H NMR evidence,Chin.J.Chem.29(2011)1143-1148;
30. [30]
  (b)X.Zhang,Y.Xiong,S.T.Zhang,et al.,Aldol condensations of aldehydes and ketones catalyzed by primary amine on water,Asian J.Chem.24(2012)751-755.
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沈阳化工大学材料科学与工程学院沈阳 110142