Subscribe to RSS
DOI: 10.1055/s-2006-926262
N-Bromosuccinimide - A Selective, Mild Substitute for Bromine
Publication History
Publication Date:
06 February 2006 (online)
Biographical Sketches
Introduction
N-Bromosuccinimide (NBS) is commercially available but can also be prepared from succinimide by bromination under alkaline conditions. It is used as a mild source of bromine with higher selectivity, primarily due to its property of releasing of bromine in a low, steady-state concentration. [1] It is most widely used for benzylic and allylic brominations in the presence of a catalytic amount of a free-radical initiator such as benzoyl peroxide or AIBN in CCl4. [2a] However, benzylic bromination in the absence of any free-radical initiator was recently achieved under microwave irradiation (MWI) in solid phase. [2b] The free-radical condition is also reported to bring about Z- to E-alkene isomerisation. [2c] Cook and co-workers demonstrated the regioselectivity of bromination by NBS under different conditions with indoles. [2a] In many instances, NBS has been used as an activator, for example in stereoselective glycosidation, [3a] protection [3b] and deprotection of ketals [3c] or THP ethers, [3d] and in the synthesis of diindolylalkanes. [3e] NBS is also widely used as a mild oxidant [4] as well as for oxidative cyclisations. [5] Recently, NBS was used for the mild, regioselective bromination of (hetero)aromatics in ionic liquid, [6a] [b] or for α-bromination of carbonyl compounds in the presence of NaHSO4-SiO2, [6c] or TMSOTf. [6d]
Abstracts
(A) Chakrabarty et al. recently reported the formation of an enamide double bond under benzylic bromination conditions with NBS in a concise synthesis of coscinamide B, an anti-HIV bisindolic enamide. [7] |
|
(B) Oxidation of indoles to isatins has also been accomplished by NBS; the reaction is thought to proceed via a 3,3-dibromooxindole as an intermediate. [8a] Indeed, Fuchs and Funk have isolated and used a 3-alkyl-3-bromooxindole as a key intermediate in the elegant syntheses of ()-flustramines A and C, [8b] and ()-perphoramidine. [8c] |
|
(C) Decarboxylative bromination with NBS in the presence of LiOAc under MWI has provided a stereoselective synthesis of (E)-β-arylvinyl bromides by a Hunsdiecker-type reaction. [9] |
|
(D) Recently, NBS was used to catalyse both hydroamination and hydroalkoxylation of activated styrenes to afford amino and ether derivatives, respectively. [10] |
|
(E) Interestingly, NBS, along with DBU, promotes the cyclisation of N-alkylthioureidoindoles and alkyl N-(indol-5′-yl)dithiocarbamates to furnish only the corresponding 2-alkylamino- and 2-alkylthiothiazolo[5,4-e]indoles, regioselectively. [11] |
|
(F) NBS has also found application in the oxidative cycloamination of olefins with aziridines for the synthesis of saturated nitrogen-contaning heterocycles. [12] |
|
- 1
March J. Advanced Organic Chemistry 4th ed.: Wiley; New York: 1992. p.1495 -
2a
Zhang P.Liu R.Cook JM. Tetrahedron Lett. 1995, 36: 3103 -
2b
Goswami S.Dey S.Jana S.Adak AK. Chem. Lett. 2004, 33: 916 -
2c
Baag M.Kar A.Argade NP. Tetrahedron 2003, 59: 6489 -
3a
Fukase K.Hasuoka A.Kinoshita I.Aoki Y.Kasumoto S. Tetrahedron 1995, 51: 4923 -
3b
Karimi B.Hazarkhani H.Maleki J. Synthesis 2005, 279 -
3c
Iranpoor N.Firouzabadi H.Shaterian HR. Tetrahedron Lett. 2003, 44: 4769 -
3d
Narender M.Somi Reddy M.Rama Rao K. Synthesis 2004, 1741 -
3e
Koshima H.Matsusaka W. J. Heterocycl. Chem. 2002, 39: 1089 -
4a
Surendra K.Krishnaveni NS.Pavan Kumar V.Sridhar R.Rama Rao K. Tetrahedron Lett. 2005, 46: 4581 -
4b
Somi Reddy M.Narender M.Rama Rao K. Tetrahedron Lett. 2005, 46: 1299 -
4c
Somoahin KV.Kudryavtsev KV. Tetrahedron Lett. 1994, 35: 7413 -
5a
Ohno M.Spande TF.Witkop B. J. Am. Chem. Soc. 1968, 90: 6521 -
5b
Sakurai O.Takashahi M.Ogiku T.Hayashi M.Horikawa H.Iwasaki T. Tetrahedron Lett. 1994, 35: 6317 -
5c
Monde K.Tamura K.Takasugi M.Kobayashi K.Somei M. Heterocycles 1994, 38: 263 -
6a
Rajagopal R.Jarikote DV.Lahoti RJ.Daniel T.Srinivasan KV. Tetrahedron Lett. 2003, 44: 1815 -
6b
Ganguly NC.De P.Dutta S. Synthesis 2005, 1103 -
6c
Das B.Venkateswarlu K.Mahender G.Mahender I. Tetrahedron Lett. 2005, 46: 3041 -
6d
Guha SK.Wu B.Kim BS.Baik W.Koo S. Tetrahedron Lett. 2006, 47: 291 - 7
Chakrabarty M.Basak R.Harigaya Y. Synthesis 2003, 2011 -
8a
Tatsugi J.Zhiwei T.Izawa Y. Arkivoc 2001, (i), 67; www.arkat-usa.org -
8b
Fuchs JR.Funk RL. Org. Lett. 2005, 7: 677 -
8c
Fuchs JR.Funk RL. J. Am. Chem. Soc. 2004, 126: 5068 - 9
Kuang C.Yang Q.Senboku H.Tokuda M. Synthesis 2005, 1319 - 10
Talluri SK.Sudalai A. Org. Lett. 2005, 7: 855 - 11
Chakrabarty M.Kundu T.Arima S.Harigaya Y. Tetrahedron Lett. 2005, 46: 2865 - 12
Sasaki M.Yudin AK. J. Am. Chem. Soc. 2003, 125: 14242
References
- 1
March J. Advanced Organic Chemistry 4th ed.: Wiley; New York: 1992. p.1495 -
2a
Zhang P.Liu R.Cook JM. Tetrahedron Lett. 1995, 36: 3103 -
2b
Goswami S.Dey S.Jana S.Adak AK. Chem. Lett. 2004, 33: 916 -
2c
Baag M.Kar A.Argade NP. Tetrahedron 2003, 59: 6489 -
3a
Fukase K.Hasuoka A.Kinoshita I.Aoki Y.Kasumoto S. Tetrahedron 1995, 51: 4923 -
3b
Karimi B.Hazarkhani H.Maleki J. Synthesis 2005, 279 -
3c
Iranpoor N.Firouzabadi H.Shaterian HR. Tetrahedron Lett. 2003, 44: 4769 -
3d
Narender M.Somi Reddy M.Rama Rao K. Synthesis 2004, 1741 -
3e
Koshima H.Matsusaka W. J. Heterocycl. Chem. 2002, 39: 1089 -
4a
Surendra K.Krishnaveni NS.Pavan Kumar V.Sridhar R.Rama Rao K. Tetrahedron Lett. 2005, 46: 4581 -
4b
Somi Reddy M.Narender M.Rama Rao K. Tetrahedron Lett. 2005, 46: 1299 -
4c
Somoahin KV.Kudryavtsev KV. Tetrahedron Lett. 1994, 35: 7413 -
5a
Ohno M.Spande TF.Witkop B. J. Am. Chem. Soc. 1968, 90: 6521 -
5b
Sakurai O.Takashahi M.Ogiku T.Hayashi M.Horikawa H.Iwasaki T. Tetrahedron Lett. 1994, 35: 6317 -
5c
Monde K.Tamura K.Takasugi M.Kobayashi K.Somei M. Heterocycles 1994, 38: 263 -
6a
Rajagopal R.Jarikote DV.Lahoti RJ.Daniel T.Srinivasan KV. Tetrahedron Lett. 2003, 44: 1815 -
6b
Ganguly NC.De P.Dutta S. Synthesis 2005, 1103 -
6c
Das B.Venkateswarlu K.Mahender G.Mahender I. Tetrahedron Lett. 2005, 46: 3041 -
6d
Guha SK.Wu B.Kim BS.Baik W.Koo S. Tetrahedron Lett. 2006, 47: 291 - 7
Chakrabarty M.Basak R.Harigaya Y. Synthesis 2003, 2011 -
8a
Tatsugi J.Zhiwei T.Izawa Y. Arkivoc 2001, (i), 67; www.arkat-usa.org -
8b
Fuchs JR.Funk RL. Org. Lett. 2005, 7: 677 -
8c
Fuchs JR.Funk RL. J. Am. Chem. Soc. 2004, 126: 5068 - 9
Kuang C.Yang Q.Senboku H.Tokuda M. Synthesis 2005, 1319 - 10
Talluri SK.Sudalai A. Org. Lett. 2005, 7: 855 - 11
Chakrabarty M.Kundu T.Arima S.Harigaya Y. Tetrahedron Lett. 2005, 46: 2865 - 12
Sasaki M.Yudin AK. J. Am. Chem. Soc. 2003, 125: 14242