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Synlett 2011(7): 887-890  
DOI: 10.1055/s-0030-1259719
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Efficient Approach to Alkenyl Nitriles from Allyl Esters

Wang Zhoua,b, Jiaojiao Xub, Liangren Zhangb, Ning Jiao*b,c
a College of Chemical Engineering, Xiangtan University, Hunan 411105, P. R. of China
b State Key Laboratory of Natural and Biomimetic Drugs, Peking University, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing 100191, P. R. of China
Fax: +86(10)82805297; e-Mail: jiaoning@bjmu.edu.cn;
c State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai 200032, P. R. of China
Further Information

Publication History

Received 2 December 2010
Publication Date:
10 March 2011 (online)

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Abstract

A novel and efficient approach to alkenyl nitriles from allyl esters has been developed. A tandem Pd-catalyzed substitution and the subsequent oxidative rearrangement are involved in this transformation. The method provides an important supplement for the synthesis of alkenyl nitriles from allyl esters.

Key words

alkenyl nitriles - allyl esters - allyl azides - oxidative rearrangement

    References and Notes

  • 1a Smith MB. March J. March’s Advanced Organic Chemistry: Reactions, Mechanisms, and Structure   6th ed.:  Wiley; Hoboken: 2007. 
    Google Scholar
  • 1b Fleming FF. Wang Q. Chem. Rev.  2003,  103:  2035 
    Google Scholar
  • 1c Miller JS. Manson JL. Acc. Chem. Res.  2001,  34:  563 
    Google Scholar
  • 1d Magnus PD. Scott A. Fielding MR. Tetrahedron Lett.  2001,  42:  4127 
    Google Scholar
  • 1e Fatiadi AJ. In Preparation and Synthetic Applications of Cyano Compounds   Patai S. Rappaport Z. Wiley; New York: 1983. 
    Google Scholar
  • 2a Basavaiah D. Jaganmohan Rao A. Satyanarayana T. Chem. Rev.  2003,  103:  811 
    Google Scholar
  • 2b Antonioletti R. Bonadies F. Ciammaichella A. Viglianti A. Tetrahedron  2008,  64:  4644 
    Google Scholar
  • 2c Zhang TY. O’Toole JC. Dunigan JM. Tetrahedron Lett.  1998,  39:  1461 
    Google Scholar
  • 2d Kojima S. Kawaguchi K. Matsukawa S. Uchida K. Akiba K. Chem. Lett.  2002,  170 
    Google Scholar
  • 2e Kojima S. Fukuzaki T. Yamakawa A. Murai Y. Org. Lett.  2004,  6:  3917 
    Google Scholar
  • 2f Yamakado Y. Ishigoro M. Ikeda N. Yamamoto H.
    J. Am. Chem. Soc.  1981,  103:  5568 
    Google Scholar
  • 2g Crowe WE. Goldberg DR. J. Am. Chem. Soc.  1995,  117:  5162 
    Google Scholar
  • 2h Peppe C. de Azevedo Mello P. das Chagas RP.
    J. Organomet. Chem.  2006,  691:  2335 
    Google Scholar
  • 2i Tomioka T. Takahashi Y. Vaughan TG. Yanase T. Org. Lett.  2010,  12:  2171 
    Google Scholar
  • This carbon-carbon bond also can be constructed by the carbocyanation of alkynes, see:
  • 3a Nakao Y. Oda S. Hiyama T. J. Am. Chem. Soc.  2004,  126:  13904 
    Google Scholar
  • 3b Nakao Y. Yukawa T. Hirata Y. Oda S. Satoh J. Hiyama T. J. Am. Chem. Soc.  2006,  128:  7116 
    Google Scholar
  • 3c Nakao Y. Yada A. Ebata S. Hiyama T. J. Am. Chem. Soc.  2007,  129:  2428 
    Google Scholar
  • 4a Li L.-H. Pan Z.-L. Duan X.-H. Liang Y.-M. Synlett  2006,  2094 
    Google Scholar
  • 4b Alterman M. Hallberg A. J. Org. Chem.  2000,  65:  7984 
    Google Scholar
  • 4c Moreno-Mañas M. Pleixats R. Roglans A. Synlett  1997,  1157 
    Google Scholar
  • 4d Masllorens J. Moreno-Mañas M. Pla-Quintana A. Pleixats R. Roglans A. Synthesis  2002,  1903 
    Google Scholar
  • 5a Oishi T. Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed.  2009,  48:  6286 
    Google Scholar
  • 5b Telvekar VN. Patel KN. Kundaikar HS. Chaudhari HK. Tetrahedron Lett.  2008,  49:  2213 
    Google Scholar
  • 5c Iida S. Togo H. Tetrahedron  2007,  63:  8274 
    Google Scholar
  • 5d Arote ND. Bhalerao DS. Akamanchi KG. Tetrahedron Lett.  2007,  48:  3651 
    Google Scholar
  • 6a Lohaus G. Org. Synth.  1970,  50:  18 
    Google Scholar
  • 6b Vorbrueggen H. Tetrahedron Lett.  1968,  9:  1631 
    Google Scholar
  • 7a Liguori A. Sindona G. Romeo G. Uccella N. Synthesis  1987,  168 
    Google Scholar
  • 7b Wood JL. Khatri NA. Weinreb SM. Tetrahedron Lett.  1979,  4907 
    Google Scholar
  • 8a Ishihara K. Furuya Y. Yamamoto H. Angew. Chem. Int. Ed.  2002,  41:  2983 
    Google Scholar
  • 8b Kuo C.-W. Zhu J.-L. Wu J.-D. Chu C.-M. Yao C.-F. Shia K.-S. Chem. Commun.  2007,  301 
    Google Scholar
  • 8c Zhou S. Addis D. Das S. Junge K. Beller M. Chem. Commun.  2009,  4883 
    Google Scholar
  • 9a Yamaguchi K. Fujiwara H. Ogasawara Y. Kotani M. Mizuno N. Angew. Chem. Int. Ed.  2007,  46:  3922 
    Google Scholar
  • 9b Yadav LDS. Srivastava VP. Patel R. Tetrahedron Lett.  2009,  50:  5532 
    Google Scholar
  • 9c Singh MK. Lakshman MK.
    J. Org. Chem.  2009,  74:  3079 
    Google Scholar
  • 9d Saha D. Saha A. Ranu BC. Tetrahedron Lett.  2009,  50:  6088 
    Google Scholar
  • 10a Rudler H. Denis B. Chem. Commun.  1998,  2145 
    Google Scholar
  • 10b Altamura A. Daccolti L. Detomaso A. Dinoi A. Fiorentino M. Fusco C. Curci R. Tetrahedron Lett.  1998,  39:  2009 
    Google Scholar
  • 10c Fernandez R. Gasch C. Lassaletta JM. Llera JM. Vazquez J. Tetrahedron Lett.  1993,  34:  141 
    Google Scholar
  • 11a Zhou W. Zhang L. Jiao N. Angew. Chem. Int. Ed.  2009,  48:  7094 
    Google Scholar
  • 11b Zhou W. Xu J. Zhang L. Jiao N. Org. Lett.  2010,  12:  2888 
    Google Scholar
  • 11c Qin C. Jiao N. J. Am. Chem. Soc.  2010,  132:  15893 
    Google Scholar
  • 12a Trost BM. Crawley ML. Chem. Rev.  2003,  103:  2921 
    Google Scholar
  • 12b Tsuji J. In Handbook of Organopalladium Chemistry for Organic Synthesis   Negishi E.-I. de Meijere A. John Wiley and Sons; New York: 2002.  p.1669 
    Google Scholar
  • 12c Trost BM. Fandrick DR. Aldrichimica Acta  2007,  40:  59 
    Google Scholar
  • 12d Trost BM. Machacek MR. Aponick A. Acc. Chem. Res.  2006,  39:  747 
    Google Scholar
  • 12e Trost BM. Van Vranken DL. Chem. Rev.  1996,  96:  395 
    Google Scholar
  • 12f Lamblin M. Nassar-Hardy L. Hierso J.-C. Fouquet E. Felpin F.-X. Adv. Synth. Catal.  2010,  352:  33 
    Google Scholar
  • 12g Murahashi S. Tanigawa Y. Imada Y. Taniguchi Y. Tetrahedron Lett.  1986,  27:  227 
    Google Scholar
  • For Pd-catalyzed allylic substitution reactions with TMSN3, see:
  • 13a Safi M. Fahrang R. Sinou D. Tetrahedron Lett.  1990,  31:  527 
    Google Scholar
  • 13b Murahashi S. Taniguchi Y. Imada Y. Tanigawa Y. J. Org. Chem.  1989,  54:  3292 
    Google Scholar
  • 13c Chang H.-M. Cheng C.-H. J. Chem. Soc., Perkin Trans. 1  2000,  22:  3799 
    Google Scholar
  • 13d Gyoung Y. Shim J.-G. Yamamoto Y. Tetrahedron Lett.  2000,  41:  4193 
    Google Scholar
  • 15a Li C.-J. Acc. Chem. Res.  2009,  42:  335 
    Google Scholar
  • 15b Buckle DR. Encyclopaedia of Reagent for Organic Synthesis   Vol. 3:  Paquette LA. John Wiley and Sons; Chichester: 1995.  p.1699 
    Google Scholar
  • 15c Walker D. Hiebert JD. Chem. Rev.  1967,  67:  153 
    Google Scholar
  • 15d Li Y.-Z. Li B.-J. Lu X.-Y. Lin S. Shi Z.-J. Angew. Chem. Int. Ed.  2009,  48:  3817 
    Google Scholar
  • 15e Zhang Y. Li C.-J. Angew. Chem. Int. Ed.  2006,  45:  1949 
    Google Scholar
  • 15f Zhang Y. Li C.-J. J. Am. Chem. Soc.  2006,  128:  4242 
    Google Scholar
  • 16a Lang S. Murphy JA. Chem. Soc. Rev.  2006,  35:  146 
    Google Scholar
  • 16b Sprecher M. Kost D. J. Am. Chem. Soc.  1994,  116:  1016 
    Google Scholar
  • 16c Katz CE. Aubé J. J. Am. Chem. Soc.  2003,  125:  13948 
    Google Scholar
  • 16d Gorin DJ. Davis NR. Toste FD. J. Am. Chem. Soc.  2005,  127:  11260 
    Google Scholar
  • 16e Yao L. Aubé J. J. Am. Chem. Soc.  2007,  129:  2766 
    Google Scholar
  • 16f Lamani M. Prabhu KR. Angew. Chem. Int. Ed.  2010,  49:  6622 
    Google Scholar
  • Other methods for the synthesis of nitriles from azide compunds:
  • 17a Hernández R. Leõn EI. Moreno P. Suárez E. J. Org. Chem.  1997,  62:  8974 
    Google Scholar
  • 17b Sasson R. Rozen S. Org. Lett.  2005,  7:  2177 
    Google Scholar
  • 17c Chiba S. Zhang L. Ang GY. Hui BW.-Q. Org. Lett.  2010,  12:  2052 
    Google Scholar
  • 18 Richard JP. Amyes TL. Lee YG. Jagannadham V. J. Am. Chem. Soc.  1994,  116:  10833 
    CrossrefGoogle Scholar
14

Typical Experimental Procedure for the Synthesis of Alkenenitriles 2 from Allyl Esters
An oven-dried Schlenk tube was charge with allyl esters (0.5 mmol), TMSN3 (0.75 mmol), Pd(PPh3)4 (0.025 mmol), and DCE (2 mL) under N2. The tube was evacuated and refilled with N2 at -40 ˚C for three times. The mixture was stirred under reflux for 1 h. Then, sulfur (0.1 mmol) and DDQ (0.75 mmol) were added subsequently and carefully under N2 atmosphere (Caution! N2 emitted violently). The mixture was stirred under reflux for proper time monitored by TLC, followed by subsequent workup as above. The reaction was cooled down to r.t. After removal of the solvent, the residue was purified by flash chromatography on silica gel (EtOAc-PE, 1:20) to obtain the desired products 2.