SYNTHESIS OF FLUOROALKYL METHYL THIOETHERS BY FORMAL ADDITION OF METHANESULFENYL FLUORIDE TO ALKENES

被引:43
作者
HAUFE, G [1 ]
ALVERNHE, G [1 ]
ANKER, D [1 ]
LAURENT, A [1 ]
SALUZZO, C [1 ]
机构
[1] UNIV LYON 1,CHIM ORGAN LAB 3,F-69622 VILLEURBANNE,FRANCE
关键词
D O I
10.1021/jo00028a056
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The electrophilic anti-1,2-addition of the elements of methanesulfenyl fluoride to carbon-carbon double bonds by a one-pot reaction of dimethyl(methylthio)sulfonium tetrafluoroborate and triethylamine trishydrofluoride with various types of alkenes is used for the synthesis of beta-fluoroalkyl methyl thioethers. This reaction is stereospecific: starting from cis-cycloalkenes (1) trans-1-fluoro-2-(methylthio)cycloalkanes (2) are formed, while trans-cyclododecene (3) gives the cis product 4 everytime in good yields. With unsymmetrical alkenes these reactions proceed regioselectively to produce Markovnikov-oriented fluoro thioethers. With 2,6-norbornadiene (26) exclusive exo attack on one double bond and subsequent transannular participation of the second pi-bond gives rise to two isomeric 3,5-disubstituted nortricyclanes, 28 and 29, while starting from the medium-sized cis,cis-1,5-cyclooctadiene (10) no transannular pi-participation is observed: the trans-1,2-addition product to one of the two double bonds in 11 is isolated. In contrast, in the reaction of the monoepoxide 30 of this diene in addition to the simple 1,2-adduct 31 a transannular oxygen participation occurs producing three oxa bicyclic compounds 32-34. The oxidation of 1-fluoro-2-(methylthio)cyclooctane (2a) by sodium periodate yields the expected mixture of two diastereomeric 1-fluoro-2-(methylsulfinyl)cyclooctanes (36) which on pyrolysis give 3-fluorocyclooctene (37).
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页码:714 / 719
页数:6
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共 75 条
  • [1] ALS GH, 1954, J CHEM SOC, P4284
  • [2] REACTIONS OF CYCLOOCTENE COMPOUNDS WITH FLUORINATING AGENTS
    ALVERNHE, G
    LAURENT, A
    HAUFE, G
    [J]. JOURNAL OF FLUORINE CHEMISTRY, 1986, 34 (01) : 147 - 156
  • [3] NEW PROCESSES FOR THE HALOFLUORINATION OF NORBORNADIENE - STRUCTURAL REEXAMINATION OF THE PRODUCTS - EVIDENCE FOR EXCLUSIVE EXO ATTACK BY ELECTROPHILES
    ALVERNHE, G
    ANKER, D
    LAURENT, A
    HAUFE, G
    BEGUIN, C
    [J]. TETRAHEDRON, 1988, 44 (12) : 3551 - 3563
  • [4] ALVERNHE G, 1987, SYNTHESIS-STUTTGART, P562
  • [5] RING-OPENING OF AZIRIDINES BY DIFFERENT FLUORINATING REAGENTS - 3 SYNTHETIC ROUTES TO ALPHA,BETA-FLUORO AMINES WITH DIFFERENT STEREOCHEMICAL PATHWAYS
    ALVERNHE, GM
    ENNAKOUA, CM
    LACOMBE, SM
    LAURENT, AJ
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 1981, 46 (24) : 4938 - 4948
  • [6] ARANDA G, 1965, B SOC CHIM FR, P1890
  • [7] ARANDA G, 1966, B SOC CHIM FR, P2850
  • [8] Banks R. E., 1982, PREPARATION PROPERTI
  • [9] THE STEREOCHEMISTRY OF STEROIDS .4. THE CONCEPT OF EQUATORIAL AND POLAR BONDS
    BARTON, DHR
    ROSENFELDER, WJ
    [J]. JOURNAL OF THE CHEMICAL SOCIETY, 1951, (APR): : 1048 - 1054
  • [10] CAPOZZI G, 1975, TETRAHEDRON LETT, P2603