Synthesis of N,N′‐Disulfonylamidines from Sulfonamides and Alkynes by a Two‐Step, One‐Pot Reaction with Nonafluorobutanesulfonyl Azide

  1. José Ramón Suárez 1
  2. Joanna Kwiczak 1
  3. Katarzyna Grenda 1
  4. M. Luisa Jimeno 2
  5. Jose Luis Chiara 1
  1. 1 Instituto de Química Orgánica General, IQOG-CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain
  2. 2 Centro de Química Orgánica “Lora Tamayo”, CENQUIOR-CSIC, Juan de la Cierva 3, E-28006 Madrid, Spain
Aldizkaria:
Advanced Synthesis & Catalysis

ISSN: 1615-4150 1615-4169

Argitalpen urtea: 2013

Alea: 355

Zenbakia: 5

Orrialdeak: 913-918

Mota: Artikulua

DOI: 10.1002/ADSC.201201001 GOOGLE SCHOLAR lock_openSarbide irekia editor

Beste argitalpen batzuk: Advanced Synthesis & Catalysis

Laburpena

Nonafluorobutanesulfonyl azide is an advantageous alternative to triflyl azide for the efficient synthesis of sulfonyl azides from sulfonamides in terms of its higher reactivity, lower cost, and non-hazardous nature. The reagent has proven its utility in a novel synthesis of N,N′-disulfonylamidines from available sulfonamides by a copper-catalyzed two-step, one-pot sequential process with added terminal alkynes.

Erreferentzia bibliografikoak

  • 10.1080/10426500490274673
  • 10.1002/ange.200902785
  • 10.1002/anie.200902785
  •  
  • 10.1021/ja00996a036
  • 10.1021/jo00795a052
  • 10.1002/hlca.19910740842
  • 10.1021/ja0264605
  • 10.1021/ol034919
  • 10.1021/ja01037a016
  • 10.1021/jo00160a024
  •  
  • 10.1002/chem.200400027
  • 10.1002/chem.200802710
  • Hoefling S. B., (2011), Synthesis, pp. 173
  •  
  • 10.1016/j.ccr.2005.10.002
  • 10.1039/c005219c
  • 10.1002/chem.201000581
  • 10.1021/ja303527m
  • 10.1021/jo7016247
  • 10.1021/ja109732s
  • 10.1002/asia.201100340
  •  
  • 10.1002/ange.200604241
  • 10.1002/anie.200604241
  • 10.1021/ol200696q
  • 10.1021/ol102087r
  • 10.1039/B912835B
  • 10.1002/adsc.200800291
  • 10.1016/j.tet.2011.06.017
  • 10.1021/jo800733p
  •  
  • 10.1021/ja0432968
  • 10.1021/ja056399e
  • 10.1002/ange.200503805
  • 10.1002/anie.200503805
  • 10.1039/c2ob25226k
  • 10.1002/ange.200503936
  • 10.1002/anie.200503936
  • 10.1021/ol061685w
  • 10.1021/ol060056j
  • 10.1002/ange.200604358
  • 10.1002/anie.200604358
  • 10.1021/ol702241e
  • 10.1002/ange.200705940
  • 10.1002/anie.200705940
  • 10.1021/ol900023t
  • 10.1039/c0cc00941e
  • 10.1002/adsc.200900706
  • 10.1002/ange.201004685
  • 10.1002/anie.201004685
  •  
  • 10.1016/j.tetlet.2010.11.135
  • Xiong W., (2011), Synthesis, pp. 1142
  • 10.1002/cjoc.201180438
  • 10.1039/c1cc11176k
  • 10.1021/ol102775s
  • 10.1016/j.tet.2010.11.094
  • 10.1002/adfm.201101153
  • 10.1021/ol201653j
  • 10.1016/j.tet.2011.08.067
  • 10.1021/ol202164x
  • 10.1039/c0cc04922k
  • 10.1016/j.tetlet.2011.12.041
  • 10.1016/j.tetlet.2012.01.083
  • 10.1021/jo300855f
  •  
  • 10.1039/b904091a
  • 10.2174/138527209789630497
  • Lu P., (2010), Synlett, pp. 165
  • 10.1002/ange.201104807
  • 10.1002/anie.201104807
  • 10.1021/ja2104203
  • 10.1021/ja210180q
  •  
  • 10.1039/c2cs15288f
  • 10.1002/9780470740859.ch3
  • 10.1016/S0065-3055(08)00003-8
  • 10.1070/RC2006v075n05ABEH001201
  • 10.1039/b515490a
  •  
  • 10.1021/ja0619096
  • 10.1021/ja301430h
  • 10.1021/ja108514t
  • 10.1021/ja062430g
  • 10.1021/ja034535e
  • 10.1002/chem.200400152
  • 10.1002/ange.19971090122
  • 10.1002/anie.199701021
  •  
  • 10.1016/j.bmcl.2009.11.104
  • 10.1002/cmdc.201100150
  • 10.1021/jm070829p
  • 10.1021/jo01039a004
  • 10.1055/s-0030-1261232
  • Kim J.‐G., (2008), Synlett, pp. 2885
  • 10.1021/ja00395a024
  • 10.1055/s-2008-1072568
  • 10.1021/ol8011088
  • NfN3is readily obtained in good yield by reaction of sodium azide with nonafluorobutanesulfonyl fluoride (nonaflyl fluoride NfF) a bulk product that is remarkably cheaper than common triflating reagents. NfN3is a colourless liquid with a characteristic pungent odour resembling that of TfN3and is stable at room temperature as a neat reagent with a reported decomposition temperature of around 120 °C:
  • Volkov N. D., (1982), Zhur. Org. Khim., 18, pp. 519
  • 10.1016/S0040-4039(00)79026-5
  • 10.1039/p19940002077
  •  
  • Yekta S., (2007), Synlett, pp. 2069
  • 10.1002/chem.200902422
  • 10.1002/adsc.201000417
  • 10.1002/adsc.201000846
  • 10.1002/1521-3757(20020715)114:14<2708::AID-ANGE2708>3.0.CO;2-0
  • 10.1002/1521-3773(20020715)41:14<2596::AID-ANIE2596>3.0.CO;2-4
  • 10.1039/B417327A
  • 10.1021/jo1009883
  • We have not included in the calculations the correspondingZZisomers which are expected to be of much higher energy than the rest due to the unfavorable steric and polar interactions between the spatially close sulfonyl groups.
  • (1991), The Chemistry of Amidines and Imidates
  • The1H‐1H ROESY (500 MHz CDCl3) spectrum of compound3f(see the Supporting Information) shows cross‐correlation peaks between the aromatic and aliphatic protons of the major species present in solution which is in agreement with the predominance of theZE‐Nf(imino) tautomer predicted by the DFT calculations in gas phase for the model disulfonylamidine.
  •  
  • 10.1039/B204172C
  • 10.1021/jo060031y