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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 16, 1986 - Issue 12
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Original Articles

Deoxygenation of Acetylenic Carbinols. Reduction of Cobalt Carbonyl Adducts with Borane-Methyl Sulfide and Trifluoroacetic Acid

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Pages 1535-1549 | Published online: 06 Dec 2006

References

  • Schuster , H. F. and Coppola , G. M. 1984 . Allenes in Organic Synthesis , 12 – 16 . 247 252 – 253 . 280 – 281 . New York : Wiley‐Interscience .
  • Theron , F. , Verny , M. and Vessiere , R. 1978 . “ Chapter 10 ” . In The Chemistry of the Carbon‐Carbon Triple Bond , Edited by: Patai , S. Chichester : Wiley . Part 1
  • Huntsman , W. D. 1980 . “ Chapter 15 ” . In The Chemistry of Ketenes, Allenes and Related Compounds , Edited by: Patai , S. Chichester : Wiley . Part 2
  • Wotiz , J. H. 1969 . “ Chapter 7 ” . In Chemistry of Acetylenes , Edited by: Viehe , H. G. New York : Marcel Dekker .
  • Schiavelli , M. D. 1980 . The Chemistry of Ketenes, Allenes and Related Compounds , Edited by: Patai , S. 426 – 427 . Chichester : Wiley . Part 1
  • Colas , Y. , Cazes , B. and Gore , J. 1984 . Tetrahedron Lett. , 25 : 845
  • Hodes , H. D. and Nicholas , K. M. 1978 . Tetrahedron Lett. , 4349
  • Lockwood , R. F. and Nicholas , K. M. 1977 . Tetrahedron Lett. , : 4163
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  • Nicholas , K. M. , Mulvaney , M. and Bayer , M. 1980 . J. Am. Chem. Soc. , 102 : 2508
  • Padmanabhan , S. and Nicholas , K. M. 1982 . Tetrahedron Lett. , 23 : 2555 For more recent work, see:
  • Padmanabhan , S. and Nicholas , K. M. 1983 . Tetrahedron Lett. , 24 : 2239
  • Saha , M. and Nicholas , K. M. 1984 . J. Org. Chem. , 49 : 417
  • Jaffer , H. J. and Pauson , P. L. 1983 . J. Chem. Res. , : 2201
  • Schegolev , A. A. , Smit , W. A. , Kalyan , Y. B. , Krimer , M. Z. and Caple , R. 1982 . Tetrahedron Lett. , 23 : 4419
  • Maryanoff , B. E. , McComsey , D. F. and Nortey , S. O. 1981 . J. Org. Chem. , 46 : 355
  • Maryanoff , B. E. and McComsey , D. F. 1978 . J. Org. Chem. , 43 : 2733
  • Nicholas , K. M. and Siegel , J. 1985 . J. Am. Chem. Soc. , 107 : 4999
  • Sternberg , H. W. , Greenfield , H. , Friedel , R. A. , Wotiz , J. , Markby , R. and Wender , I. 1954 . J. Am. Chem. Soc. , 76 : 1457
  • O‐Yang , C. and Fried , J. 1983 . Tetrahedron Lett. , 24 : 2533 Uncomplexed, the Z and E isomers of 1 were inseparable by tlc. Such cobalt complexes have been reported to facilitate separation of inseparable acetylenic prostaglandins:
  • Gribble , G. W. , Leese , R. M. and Evans , B. E. 1977 . Synthesis , : 172
  • Anyway, primary acetylenic carbinols are probably the easiest to deoxygenate by conventional techniques without allene production, e. g., see:
  • Hutchins , R. O. , Kandasamy , D. , Maryanoff , C. A. , Masalamani , D. and Maryanoff , B. E. 1977 . J. Org. Chem. , 42 : 82
  • Hutchins , R. O. , Kandasamy , D. , Dux , F. III , Maryanoff , C. A. , Rotstein , D. , Goldsmith , B. , Burgoyne , W. , Cistone , F. , Dalessandro , J. and Puglis , J. 1978 . J. Org. Chem. , 43 : 2259
  • For elimination reactions of cobalt‐acetylenic carbinol complexes, see:
  • ref 5, footnote 17
  • Connor , R. E. and Nicholas , K. M. 1977 . J. Organometal. Chem. , 125 : C45
  • The chemoselectivity of bis(trifluoroacetoxy)borane makes it quite favorable for selective reductions.4
  • Mp 152–153°C (2‐propanol); satisfactory C, H, and N analyses
  • Maryanoff , B. E. 1984 . J. Med. Chem. , 27 : 843 Prepared according to the styrene oxide procedure in:
  • The lactol from phthalide was condensed with Ph3, P=CH(CH2),3COO−Li+ (Maryanoff, B. E. and Duhl‐Emswiler, B. A., Tetrahedron Lett., 1981, 22, 4185), and the product (E/Z = 35:65) was photoisomerized (PhSSPh, sunlamp), esterified (CH3OH, BF3.Et2O), oxidized (pyridinium chlorochromate), and reacted with hexynyl‐magnesium bromide to give 1 (oil; E/Z = 90:10), characterized by 1H NMR and mass spec. (C and H analysis on the parent acid)

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