Sulfur Reagents in Organic Synthesis

Автор(ы):Metzner P., Thuiller A.
06.10.2007
Год изд.:1994
Описание: «The aim of this book, which we purposely wanted to keep small in size, is to present some aspects of the chemistry of sulfur reagents. We have selected a few excerpts, and we are aware that our choices are arbitrary— to give hints on the tremendous, and still largely unexplored, potentiality of sulfur-mediated synthesis, particularly for complex molecules, with examples of the very recent literature (more than one-third of the experimental procedures given in the text were published in 1991-1993). were our main guides. Yields, selectivities (chemo-, regio- and stereoselectivity), scale and scope of the reactions were taken into consideration, and in some cases our personal views on their interest. We hope that the reader will share our enthusiasm for sulfur chemistry and think of using it in his or her daily work.»
Оглавление:
Sulfur Reagents in Organic Synthesis — обложка книги.
1 Introduction [1]
2 Preparation of organosulfur reagents [3]
  2.1 Thiols [3]
    1,2-Benzenedithiol [3]
  2.2 Sulfides [6]
    Thiolation of aldehydes and ketones: general procedure [7]
    Sulfides by addition ofthiols to alkenes [8]
    1,4,7,11,14,17-Hexathiaicosane [9]
  2.3 Disulfides and polysulfides [10]
    Ethyl 2-pyridyl disulfide [11]
    2-(Ethldithio)hexadecanoic acid [11]
    Dimethyl trisulfide (R=Me) [12]
  2.4 Thio- and dithioacetals and related compounds [12]
    2-(2-Furyl)-1,3-dithiane [13]
    Clayfen reagent [14]
    Cleavage of dithioacetals by clay-supported metal nitrates [15]
    Cleavage ofdithiolans by t-BuBr/DMSO [16]
    Transthioacetalization with 4-nitrobenzaldehyde [16]
    Асуl silanes by anodic oxidation of 2-alkyl-2-trialkylsilyl-1,3-dithianes [17]
    Photolytic transformation of dithioacetals into carbonyl compounds [18]
  2.5 Ketenedithioacetals and a-oxoketenedithioacetals [19]
    Bis(dimethylaluminium) 1,3-propanedithiolate [20]
    2-(3-Cyclohexenylidene)-1,3-duhiane [21]
    1,1-Bis(methylthio)-1,3-butadiene and 3-methyl-1,1-bis(methylthio)-1,3-butadiene [22]
  2.6 Sulfoxides [23]
      2.6.1 Oxidation of sulfides [23]
    1,3-Dithiane-1-oxide [24]
    1,3-Dithiane-1,1-dioxide [24]
      2.6.2 Asymmetric synthesis of sulfoxides [25]
    (1R,2S,5R)-(-)-Menthyl(S)-p-toluenesulfinate [26]
    (R)-(+)-Methylp-tolylsulfoxide [26]
  2.7 Sulfones [28]
    (E)-Styryl p-tolyl sulfone [29]
  2.8 Thiocarbonyl compounds [30]
      2.8.1 Thioaldehydes [30]
    Silicon-assisted synthesis of thioaldehydes and trapping [31]
      2.8.2 Thioketones [32]
    Di-t-butyl ketone imine [33]
    Di-t-butyl thioketone [34]
    (-)-Thiocamphor [34]
    2,6-Dimethylheptane-4-thione [35]
    Selective synthesis of enethiols [36]
      2.8.3 Thionoesters and dithioesters [36]
    General procedure for the reactions of esters with Lawesson's reagent [38]
    Conversion ofpropanoic acid into methyl propanedithioate with Davy's reagent (R(?)=Me) [39]
    Preparation of dithioacetic acid by addition of methylmagnesium iodide to carbon disulfide [40]
    General procedure for the preparation of dithioesters from CS2 and Grignard reagents [41]
    Phenyl 4-pentenedithioate [42]
    Synthesis of saturated and unsaturated dithioesters through reaction of Grignard reagents with phenylisothiocyanate, alkylation and sulfhydrolysis [43]
      2.8.4 Thioamides [44]
    N,N-Diethylthioacetamide [45]
      2.8.5 Xanthates [46]
    Synthesis of O-alkyl S-methyl dithiocarbonates (xanihates) [47]
      2.8.6 Miscellaneous thiocarbonyl compounds [48]
        2.8.6.1 Thioketenes [48]
        2.8.6.2 Isothiocyanates [49]
    Cyclohexyl isothiocyanate [49]
        2.8.6.3 Sulfines and sulfenes [50]
  2.9 Sulfonium salts and sulfur ylides [51]
3 Functional modifications with organosulfur compounds [53]
  3.1 Introduction of unsaturation [53]
      3.1.1 Creation of a double bond a to a carbonyl group [54]
    Oxidation of diphenyl disulfide with chloramine [54]
    2-(Phenylthio)cyclooctanone [55]
    Methyl 2-pyridinesulfinate [55]
    Sulfinylation ofketones and elimination [57]
      3.1.2 Alkenes from 1,2-dihalo compounds [57]
    Dehydrohalogenation of meso-1,2-dibromo-1,2-diphenylethane [57]
      3.1.3 Alkenes from 1,2-diols [58]
    Alkenes from vic-dixanthates [59]
  3.2 Radical deoxygenation of alcohols: the Barton reaction [60]
    Cholestane from a cholestanol thionocarbonate [61]
  3.3 Oxidation of alcohols [ 62]
  3.4 Asymmetric reduction [63]
      3.4.1 Sulfinyl-induced asymmetric reduction [63]
      3.4.2 p-Hydroxysulfoximine-catalysed enantioselective reduction of ketones [63]
  3.5 Decarboxylation [64]
  3.6 The Pummerer rearrangement [64]
    (1 R,5R)-6,6-Dimethyl-3-(phenylthio)bicyclo[3.1.1]hept-3-еn-2-оnе [66]
  3.7 Miscellaneous reactions [67]
    Deracemization of a terpenic thiolester [69]
    Fluorination of methyl arenedithiocarboxylates [69]
    Fluorination of thionesters with DAST [71]
    Conversion ofsulfones to aldehydes or ketones [73]
4 Organosulfur compounds as intermediates in organic synthesis [75]
  4.1 A word on desulfurization [75]
  4.2 С-С bond-forming reactions [75]
      4.2.1 Use of sulfides, dithioacetals and orthotrithioesters [75]
        4.2.1.1 1,3-Dithianes as acyl anion equivalents [75]
    Ring opening ofaziridine with dithianes [77]
    Hydrolytic removal of dithiane [77]
    Propyl cyclopentyl ketone (via a borate complex of lithiobenzodithiole) [79]
        4.2.1.2 Carboxy anion equivalents [79]
    (S) - (+)-3-Hydroxy-4- (benzyloxy)tris (methylthio)methane [80]
    Methyl 3-hydroxy-4-benzyloxybutanoate [80]
        4.2.1.3 Thioacetal monoxides [81]
    Synthesis of an amino ester [82]
        4.2.1.4 a-Metallated sulfides [85]
    Preparation of a solution ofphenylthiomethyllitliium [86]
    Bis(phenylthio)methyllithium [87]
        4.2.1.5 Reductive lithiation of phenyl sulfides [89]
    Lithium p,p'-di-tert-butylbiphenytide (LDBB) [92]
    Cyclohexenyllithium by metallation of phenylthiocyclohexene [92]
    Cyclohexenyl cyclohexyl methanol [92]
        4.2.1.6 Metal-catalysed Grignard reaction with sulfides and dithioacetals [94]
    Camphene synthesis via gem-dimethylation of a dithiolane [94]
        4.2.1.7 Reactions of a-halo sulfides with silyl enolates [95]
        4.2.1.8 Lewis acid-catalysed ketene dithioacetal functionalization [96]
      4.2.2 Thiophilic versus carbophilic addition of organometallics to a C=S bond. Carbanions through thiophilic addition [96]
        4.2.2.1 Dithioesters [96]
    Thiophilic addition of Grignard reagents to methyl dithioates [97]
    Egomaketone and perillene [100]
    Ethyl 3-furandithiocarboxylate [101]
    Egomaketonedithioacetal [101]
    Egomaketone [101]
    Perillene [101]
        4.2.2.2 Thionoesters, thioketones and thioaldehydes, and thioamides [104]
    (±)-2-Ethyl-2-(methylthio)-8-hexyloxocane [104]
    (±)-cte-2-Ethyl-8-hexyloxocane(lauthisan) [105]
      4.2.3 Reactions of enethiolates [106]
      4.2.4 The aldol reaction [107]
    Synthesis of methyl 3-oxodithioalkanoates [109]
    (i) P-Hydroxydithioesters [109]
    (ii) P-Oxodithioesters [109]
      4.2.5 Michael addition [110]
    Michael addition of lithium enethiolates [111]
      4.2.6 Alkylation of thioamides [113]
      4.2.7 Thioesters and imidothioesters in C-C bond formation [113]
    One-pot thioirnidoester-mediated synthesis of tians-(+)-a-atlantone [116]
      4.2.8 Uses of sulfoxides [118]
    (?)-Ketosulfoxides [120]
    Reduction of ketosulfoxides with DIBAH [121]
    Reduction of ketosulfoxides with DIBAH in the presence ofZnCl2 [121]
    Oxidation of(RS)- and (KR)-p-hydroxysulfoxides to (S)-and (R)-suifones [121]
    Butenotides [121]
      4.2.9 Use of sulfones [123]
    Desulfonylation of alkyl or vinyl phenyl sulfones [124]
  4.3 C=C Bond-forming reactions [126]
      4.3.1 Useofsulfidesanddithioacetals [126]
      4.3.2 Sulfone-based eliminations [128]
    Preparation of an episulfone [128]
    Alkenes by reductive elimination of (?)-hydroxyimidazolyl sulfones [130]
    2-(Benzenesulfonyl)tetrahydro-2H-pyran [132]
    Condensation of the anion of 2-(benzenesulfonyl)tetrahydropyran with electrophiles [132]
    1,7-Dioxa[5.5]imdecane [132]
      4.3.3 Carbonyl methylidenation with sulfoximines and other derivatives [134]
    Alkenes from sulfoximines [134]
    Alkenyl sulfides from thiolesters [137]
      4.3.4 Two-fold extrusion [138]
      4.3.5 The Eschenmoser reaction [140]
    Thiopyrrolidone [140]
    Alkylation of thiopyrrolidone with ethyl bromoacetate; preparation of an enamine ester [140]
      4.3.6 Miscellaneous reactions [142]
  4.4 Three-membered ring-forming reactions. Cyclopropanation, formation of epoxides [143]
      4.4.1 Use of sulfur ylides [143]
    Trimethylsulfonium methyl sulfate [143]
    Styrene oxide [144]
    Synthesis of epoxides from carbonyl compounds and sulfonium salts [144]
    Synthesis ofbis(methylthio)dihydrofurans [146]
    Conversion ofbis(methylthio)dihydrofurans to (methylthio)furans [146]
    3-Phenylfuran [147]
      4.4.2 Helquist Cyclopropanation with iron-bonded sulfonium ylides [149]
    Cyclopropanation ofl,l-diphenylethene with Helquist's reagent [149]
      4.4.3 Cyclopropanation with t-butylsulfonyl methyllithium [150]
    Cyclopropanation ofalkenes with sulfonyl carbanions [151]
      4.4.4 Asymmetric synthesis with sulfur ylides [152]
    Cyclopropanation of methyl 3,3-diphenyl-2-(p-tolylsulfinyl)-2-propenoate [153]
  4.5 Pericyclic reactions of organosulfur compounds [153]
      4.5.1 The thio-Claisen rearrangement [154]
    syn-Methyl2-(1-hydroxyethyl)-pent-4-enedithioate by the thio-Claisen rearrangement [157]
    Ketene Claisen rearrangement of an allylthioether [158]
      4.5.2 [2,3] Sigmatropic processes [159]
      4.5.3 Ene and retro-ene reactions [161]
      4.5.4 Cycloaddition reactions [163]
    (±)-2-(1-t-Butyl-2,2-dimethylpropylidene)bornene [164]
        4.5.4.1 Thiocarbonyl compounds in (4 + 2) cycloaddition [164]
        4.5.4.2 Ancillary role of sulfur functionalities in cycloaddition reactions [166]
    (a) Vinyl sulfides [166]
    (b) Vinyl sulfoxides [167]
    (S)-Ethoxy p-tolyl vinyl sulfonium tetrafluoroborate [169]
    Diels—Alder reaction with cyclopentadiene [169]
    (c) Vinyl sulfones [170]
      4.5.5 Cheletropic processes [172]
    3,6-Diethyl-3,5-octadiene from a sulfolene [174]
    2-Tributylstannyl-2,5-dihydrothiophene-S-S-dioxide [177]
    (E)-1,3-Butadienyl(tributyl)stannane [177]
    (±)-Estra-1,3,5(10)-triene-17-one [178]
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