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Synthetic Communications
An International Journal for Rapid Communication of Synthetic Organic Chemistry
Volume 14, 1984 - Issue 13
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Original Articles

A Convenient Synthesis of (S)-2-Methyl and (2S)-2,3-Dimethyl Butyl Phenylsulfones from (S)-(-)-3-Methyl-γ-butyrolactone

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Pages 1199-1204 | Published online: 19 Dec 2006

References

  • Piatak , D. M. and Wicha , J. 1978 . Chem. Rev. , 78 : 199 For extensive reviews on the topic, see
  • Redapath , J. and Zeelen , F. J. 1983 . Chem. Soc. Rev. , 12 : 75
  • Schmitz , F. J. 1982 . Marine Natural Products , Edited by: Scheuer , P. J. Vol. 1 , 261 New York : Academic Press .
  • Mori , K. , Sakakibara , M. and Okada , K. 1984 . Tetrahedron , 40 : 1767 and references cited.
  • Leuenberger , H. G. W. , Boguth , W. , Barner , R. , Schmid , M. and Zell , R. 1979 . Helv. Chim. Acta , 62 : 455
  • We observed that yields of (1) by this route strongly depended on the conditions used for preparation of ethyl 4,4-dimethoxy-3-methylcrotonate namely on the base used for the Wittig reaction. We used for the condensation either EtONa, n-BuLi and NaNH2, and yields of final product (1) were 15–20%, 25–30% and 40% respectively. This fact, along with recovery of unsaturated hydroxyester which could not be reduced to the corresponding saturated compound even after one week incubation, strongly suggests that the microorganism distinguishes betwwen the two isomeric (E)- and (Z)-unsaturated esters for the reductive step
  • Reppe , W. 1955 . Liebigs Ann. Chem. , 596 : 194
  • Nambara , T. and Matsuhisa , N. 1963 . Yakagaku Zhassi , 83 : 642 (C. A., 59, 7411f)
  • Crossland , R. K. and Servis , K. L. 1970 . J. Org. Chem. , 35 : 3195
  • The sulfone (4a) could also be prepared from the sulfone-alcohol (4b) prepared from alcohol (3a) in 75% yield (m-CPBA in dichloromethane, 18 h at room temperature). Alcohol (4b) was mesylated (82%) and (4c) selectively reduced to (4a) with LiAIH4 (refluxing diethyl ether, 3 h, 55% yield of isolated product). Optical purity of final product (4a) was practically identical to that exhibited by the same product prepared from the phenylsulfide (3d) [α]D = +13.1, c 3.5 in CHCl3
  • Crombie , L. and Harper , S. H. J. Chem. Soc. , 1950 2685
  • (S)-(-)-2-Methyl-1-butanol was tosylated, the tosylate transformed into phenylsulfide (3d), which was oxidized with m-CPBA
  • Since the synthetic sequence of preparation of (4a) from (1) should not affect the chiral center, it could be inferred that the microbiological reduction is 90% enantioselective.
  • Hermann , J. J. and Schlessinger , R. H. J. Chem. Soc., Chem. Commun. , 1973 711
  • It can be assumed that α-methylation of (2) should occur with some diastereoselectivity, but we did not investigate this point since the moiety containing the new chiral center was going to be transformed in a symmetrical isopropyl group
  • Mori , K. , Sakakibara , M. , Ichikawa , Y. , Ueda , H. , Okada , K. , Umemura , T. , Yabuta , G. , Kuwahara , S. and Kondo , M. 1982 . Tetrahedron , 38 : 2099

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