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;
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Publikationsverlauf

Received 21 October 2008
Publikationsdatum:
25. Februar 2009 (online)

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.

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