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Studies on the Acid-Base Cooperative Reactions in Organotin-Catalyst Systems and Their Applications

Research Project

Project/Area Number 63470082
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionOkayama University of Science

Principal Investigator

NOZAKI Hitoshi  Okayama Univ. Sci. Engineering, Professor, 工学部, 教授 (40025763)

Co-Investigator(Kenkyū-buntansha) SATO Tsuneo  Okayama Univ. Sci. Engineering, Lecturer, 工学部, 講師 (80183383)
OTERA Junzo  Okayama Univ. Sci. Engineering, Professor, 工学部, 教授 (20131617)
Project Period (FY) 1988 – 1989
Project Status Completed (Fiscal Year 1989)
Budget Amount *help
¥7,000,000 (Direct Cost: ¥7,000,000)
Fiscal Year 1989: ¥2,100,000 (Direct Cost: ¥2,100,000)
Fiscal Year 1988: ¥4,900,000 (Direct Cost: ¥4,900,000)
Keywordsorganotin / sulfide / Lewis acid / protection / Tetrahydropyranyl ether / alcohol / ester / Carboxylic acid / ジスタノキサン / エステル交換 / ラクトン化 / アセタール化 / 有機硫化物 / チオアルコキシル化 / モノチオアセタール / ガンマ-アルコキシアリルスルフィド
Research Abstract

Studies on the behavior of organotin-sulfur reagents in the presence of Lewis acids have disclosed following points:
(1) Novel access to monothioacetals from acetals ---- Monothioacetals of the general formula of PhS-CHR-OMe are synthetically useful intermediates. However, the bottle neck to be funnelled has been the access to this type of compounds. The authors have discovered treatment of acetals RCH(OMe)_2 with Bu_3SnSPh in the presence of BF_3・OEt_2 provides the desired products.
(2) Protective activation of hydroxyl groups ---- Tetrahydropyranylation (THP) of hydroxyl groups is a well-known method of protection of a hydroxyl group. The authors have discovered that the tetrahydropyranyloxy moiety is preferentially transformed into alkoxystannanes, ROSnBu_3 and 2-phenylthio- tetrahydropyran upon treatment with Bu_3SnSPh in the presence of BF_3・OEt_2. The former tin alkoxides are easily alkylated (to ethers), acylated (to esters), and oxidized (to aldehydes and ketones) by proper treat … More ment. That is protection with THP increases the susceptibility of the hydroxyl group to these transformations. The observation will certainly find applications in the selective transformation of polyols.
(3) A new preparation of 1,3-dithianes ---- The reaction of acetals with 1,3- propanedithiols proceeds in the presence of Bu_2Sn(OTf)_2 (Tf = -OSO_2CF_3), which is a new Lewis acid first prepared by the authors, to afford good yields of 2-substituted 1,3-dithianes.
(4) Introduction of electrophilic groups on the beta-carbon of alpha- enals ---- When the reaction described in (1) above is applied to the alpha- enal acetals, RCH=CH-CH(OMe)_2, the resulting products are 1-methoxy-3- phenylthio-l-alkenes, RCHSPh-CH=CHOMe. Lithiation at the C(3) position followed by the action of electrophilic reagents (E) provides the products, RC(SPh)(E)-CH=CHOMe, whose hydrolysis and desulfurization give RC(E)=CH-CHO products. The sequence provides a means of substituting the beta C-H bond with C-E bond.
(5) Protective activation of carboxylic acids ---- The authors have disclosed a new application of alpha-methylcinnamyl esters as a way of protective activation. Treatment of this kind of esters with Bu_3SnSPh reagent in the presence of BF_3・OEt_2 affords the stannyl esters R-COOSnBu_3, which are the reactive tin salts being easily transformed into esters, free carboxylic acids, and so on. This is a way of selective activation of a carboxyl group in polycarboxylic acids. Less

Report

(3 results)
  • 1989 Annual Research Report   Final Research Report Summary
  • 1988 Annual Research Report
  • Research Products

    (23 results)

All Other

All Publications (23 results)

  • [Publications] T.Sato: "Activation and Synthetic applications of thiostannans.Chemical modification of hydrooy Sunetion under protection." Tetrahedron Letl.30. 1665-1668 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Sato: "Activation and synthetic of thiostannaves.Thioalkorylation of acetals" Tetrohedron. 45. 1209-1218 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Sato: "Activation and synthetic applications of thiostannares.Protection of carbooyl groups with α-methyl ciunamyl alcohol as ameans of chemodifferentiation and selective activation" Tetrohedron Letl.30. 2959-2962 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] J.Otera: "Unusual rate acceleration in the presence of aldelydes of chistannoxanecatalyzed acetalezation of ketones and deactivatel oldehydes" Organometallics. 8. 2063-2065 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] J.Otera: "Distannoxaue as reverse micelle-type catolystnovel solvent effect on reaction rate of trausesterification" J.Org.Chem.54. 4013-4014 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Sato: "Organotin triflate-poomoted carbonylactivation.Doesacetalzation deactivateor activate carbonyl gcoups?" J.Am.Chem.Soc.112. 901-902 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Sato, J. Otera, and H. Nozaki: "Activation and Synthetic Applications of Thiostannanes. Chemical Modification of Hydroxy Function under Protection" Tetrahedron Lett., 30, 1665-1668 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Sato, J. Otera, and H. Nozaki: "Activation and Synthetic Applications of Thiostannanes. Thioalkoxylation of Actals" Tetrahedron, 45, 1209-1218.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Sato, J. Otera, and H. Nozaki: "Activation and Synthetic Applications of Thiostannanes. Protection of Carboxyl Groups with alpha-Methylcinnamyl Alcohol as a Means of Chemical Modification and Selective Activation" Tetrahedron Lett., 30, 2959-2962 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] J. Otera, T. Mizutani, and H. Nozaki: "Unusual Rate Acceleration in the Presence of Aldehydes of Distannoxane-Catalyzed Acetalization of Ketones and Deactivated Aldehydes" Organometallics, 8, 2063-2065 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] J. Otera, S. Ioka, and H. Nozaki: "Distannoxane as Reverse Micelle-Type Catalyst: Novel Solvent Effect on Reaction Rate of Transesterification" J. Org. Chem., 54, 4013-4014 (1989).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T. Sato, J. Otera, and H. Nozaki: "Organotin Triflate-Promoted Carbonyl Activation. Does Acetalization Deactivate or Activate Carbonyl Groups?" J. Am. Chem. Soc., 112, 901-902 (1990).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1989 Final Research Report Summary
  • [Publications] T.Sato: "Activation and synthetic applications of thiostannanes Chemical modification of hydrocy function under protetion" Tetrahedron Lett. 30. 1665-1668 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Sato: "Activation and synthetic applications of thiostannanes.Thioalkoeylation of acetals" Tetrahedron. 45. 1209-1218 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Sato: "Activation and synthetic applications of thistaunanes.Potection of carboeyl glorps with αーmehul ciunamyl abohol as a means of chemclifferentiation and selective activation" Tetrahedron Lett. 30. 2959-2962 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] J.Otera: "Unusual rate acceleration in the presence of aldeluydes of distumnomue catalgzed acetalization of ketones and deactivated aldelydes" Arganometallis. 8. 2063-2065 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] J.Otera: "Distannoxane as reverse micelle type catalyst:novel solvent effect on reaction rate of transesterification" J.Org.Chem.54. 4013-4014 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] T.Sato: "Organotin triflate-promoted carfouyl activation Does acltalization deactivate or activate carbovyl groups?" J.Am.Chem.Soc.112. 901-902 (1990)

    • Related Report
      1989 Annual Research Report
  • [Publications] Tsuneo Seto.: Tetra hedron Lett.29. 2979-2982 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Tsuneo Seto.: Tetra hedron Lett.29. 3971-3974 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] Tsuneo Seto.: Tetra hedron.

    • Related Report
      1988 Annual Research Report
  • [Publications] Tsuneo Seto.: Tetra hedron Lett.

    • Related Report
      1988 Annual Research Report
  • [Publications] 野崎一: 有機合成化学協会誌.

    • Related Report
      1988 Annual Research Report

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Published: 1988-04-01   Modified: 2016-04-21  

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