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Synlett 2009(5): 739-742  
DOI: 10.1055/s-0028-1087933
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Improved Protocol for the Oxidative Cleavage of Alkynes, Alkenes, and Diols with Recyclable Ru/C

Vijay Kumar A., V. Prakash Reddy, R. Sridhar, B. Srinivas, K. Rama Rao*
Organic Chemistry Division I, Indian Institute of Chemical Technology, Hyderabad 500 007, India
e-Mail: kakulapatirama@gmail.com;
Further Information

Publication History

Received 21 October 2008
Publication Date:
25 February 2009 (online)

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Abstract

Efficient synthesis of carboxylic acids from alkynes; aldehydes from alkenes and diols employing Ru/C-based recyclable catalytic system is reported with good to excellent yields.

Key words

oxidation - Ru/C - supported catalyst - alkenes - alkynes - diols - carboxylic acids

    References and Notes

  • 1a Brinksma J. de Boer JW. Hage R. Feringa BL. In Modern Oxidation Methods   Bäckvall J.-E. Wiley-VCH; Weinheim: 2004.  p.295 
    Google Scholar
  • 1b Murahashi S.-I. Komiya N. In Biomimetic Oxidations Catalyzed by Transition Metal Complexes   Meunier B. ImperialCollege Press; London: 2000.  p.563 
    Google Scholar
  • 1c Lee TV. In Comprehensive Organic Synthesis   Vol. 7:  Trost BM. Fleming I. Ley SV. Pergamon; Oxford: 1991.  p.291 
    Google Scholar
  • 2a Griffith WP. Ley SV. Whitcombe GP. White AD. J. Chem. Soc., Chem. Commun.  1987,  179 
    Google Scholar
  • 2b Ley SV. Norman J. Griffith WP. Marsden SP. Synthesis  1994,  639 
    Google Scholar
  • 2c Ley SV. Norman J. Griffith WP. Marsden SP. J. Chem. Soc., Chem. Commun.  1987,  1625 
    Google Scholar
  • 2d Griffith WP. Chem. Soc. Rev.  1992,  21 
    Google Scholar
  • 3a Che C.-M. Yu W.-Y. Chan P.-M. Cheng W.-C. Peng S.-M. Lau K.-L. Li W.-K. J. Am. Chem. Soc.  2000,  122:  11380 
    Google Scholar
  • 3b Yip W.-P. Yu W.-Y. Zhu N. Che C.-M. J. Am. Chem. Soc.  2005,  127:  14239 
    Google Scholar
  • 3c Plietker B. Niggemann M. Org. Lett.  2003,  5:  3353 
    Google Scholar
  • 4a Yang D. Zhang C. J. Org. Chem.  2001,  66:  4814 
    Google Scholar
  • 4b Che C.-M. Yip WP. Yu W.-Y. Chem. Asian J.  2006,  1:  453 
    Google Scholar
  • 4c Yang D. Chen F. Dong Z.-M. Zhang D.-W. J. Org. Chem.  2004,  69:  209 
    Google Scholar
  • 5 Koposov AY. Karimov RR. Pronin AA. Skrupskaya T. Yusubov MS. Zhdankin VV. J. Org. Chem.  2006,  71:  9912 
    CrossrefGoogle Scholar
  • 6 Roth S. Gohler S. Huan C. Stark CBW. Eur. J. Org. Chem.  2005,  4109 
    Google Scholar
  • 7a Plietker B. J. Org. Chem.  2003,  68:  7123 
    Google Scholar
  • 7b Plietker B. Org. Lett.  2004,  6:  289 
    Google Scholar
  • 8a Mori S. Yanase T. Aoyagi S. Monguchi Y. Maegawa T. Sajiki H. Chem. Eur. J.  2008,  14:  6994 
    Google Scholar
  • 8b Zhu Y.-Z. Cai C. Eur. J. Org. Chem.  2007,  2401 
    Google Scholar
  • 8c Maegawa T. Kitamura Y. Sako S. Udzu T. Sakurai A. Tanaka A. Kobayashi Y. Endo K. Bora U. Kurita T. Kozaki A. Monguchi Y. Sajiki H. Chem. Eur. J.  2007,  13:  5937 
    Google Scholar
  • 9a Frieman BA. Taft BR. Lee C.-T. Butler T. Lipshutz BH. Synthesis  2005,  2989 
    Google Scholar
  • 9b Lipshutz BH. Frieman BA. Nihan D. Taft BR. Lee C.-T. Lower A. Chem. Asian J.  2006,  1:  417 
    Google Scholar
  • 10a Lipshutz BH. Taft BR. Angew. Chem. Int. Ed.  2006,  45:  8235 
    Google Scholar
  • 10b Lipshutz BH. Unger JB. Taft BR. Org. Lett.  2007,  9:  1089 
    Google Scholar
  • 10c Lipshutz BH. Nihan DM. Vinogradova E. Taft BR. Bosković ZV. Org. Lett.  2008,  10:  4279 
    Google Scholar
  • 11a Kantam MLR. Reddy S. Pal U. Sreedhar B. Bhargava S. Adv. Synth. Catal.  2008,  350:  2231 
    Google Scholar
  • 11b Maegawa T. Fujiwara Y. Inagaki Y. Monguchi Y. Sajiki H. Adv. Synth. Catal.  2008,  350:  2205 
    Google Scholar
  • 12 Ho MC. Yu WY. Che C.-M. Angew. Chem.  2004,  116:  3365 
    CrossrefGoogle Scholar
  • 13 Yamaguchi K. Mizuno N. Angew. Chem. Int. Ed.  2002,  41:  4538 
    CrossrefPubMedGoogle Scholar
  • 14 Kim W.-H. Park IS. Park J. Org. Lett.  2006,  8:  2543 
    CrossrefGoogle Scholar
  • 15 Choi E. Lee C. Na Y. Chang S. Org. Lett.  2002,  4:  2369 
    CrossrefGoogle Scholar
16

Typical Experimental Procedure for the Oxidation of Alkynes
Ruthenium (1 mol%, Ru/C, 20 mg), alkyne (1 mmol), Oxone (1 equiv), and NaHCO3 (2.5 equiv) were taken in a round-bottom flask (25 mL) with a magnetic stir bar. Then, a mixture of H2O-MeCN (1:1, 5 mL) was added and stirred until complete consumption of the alkyne was observed as monitored by TLC. The reaction mixture was extracted with EtOAc (3 × 10 mL), the combined organic layers were dried over anhyd Na2SO4, and concentrated to give the analyti-cally pure product.
Typical Experimental Procedure for the Oxidation of Alkenes and Diols Ruthenium (1 mol%, Ru/C, 20 mg), alkene/diol (1 mmol), and NaIO4 (214 mg, 1.1 equiv), were taken in a mixture EtOAc-MeCN-H2O (1:1:1, 4.5 mL) in a 25 mL round-bottom flask with a magnetic stir bar and stirred until complete consumption of the alkene/diol was observed as monitored by TLC. The reaction mixture was extracted with EtOAc (3 × 10 mL), the combined organic layers were dried over anhyd Na2SO4, and concentrated to give the analytically pure product.

17

Specific optical rotation of the product (+)-3-methyladipic acid was [α]D ²0 7.1 (c 5, MeOH).