Organic Reactions in Steroid Chemistry. Volume 1

Автор(ы):Fried J.
06.10.2007
Год изд.:1972
Описание: In the following years steroid research accelerated at an almost feverish pace as the utility of some of these compounds as hormonal and pharmacological agents was recognized and implemented in clinical practice. These studies led not only to a better understanding of the mechanistic and stereochemical factors involved in the reaction, but also often afforded milder and more selective experimental conditions. However, from a practical viewpoint much of this large body of knowledge is buried in the steroid literature, and is unfortunately only rarely consulted by the nonsteroid chemist who may be seeking to carry out similar transformations with other classes of compounds. It is the purpose of this book to afford a critical review covering both theoretical and experimental aspects of some of the most important and synthetically useful transformations in steroid chemistry.
Оглавление:
Organic Reactions in Steroid Chemistry. Volume 1 — обложка книги.
1 REDUCTIONS OF STEROIDS BY METAL-AMMONIA SOLUTIONS. Hugh L. Dryden, Jr.
  I. Introduction [1]
  II. Selectivity of Reduction [2]
    Protection of ketones against reduction [10]
  III. The Birch Reduction of Aromatic Steroids [11]
    Mechanism of the reduction of aromatic compounds [12]
    Factors influencing the rate of reduction [14]
    Protonation of reduction intermediates [17]
    Origin of by-products in Birch reductions [18]
    Acidity of proton donor. Effect of iron in Birch reductions [19]
    Requirements of Birch reduction procedures [22]
    Experimental conditions for Birch reductions [25]
  IV. Reduction of Conjugated Enones and Dienones, Saturated Ketones and Ketol Acetates. Reductive Alkylation [27]
    Mechanism of reduction [27]
    Stereochemistry of reduction [34]
    Side reactions in reductions [37]
    Experimental conditions for metal-ammonia reductions and reductive alkylations [43]
  V. Experimental Procedures [48]
    Method of Wilds and Nelson for Birch reduction [48]
    Birch reductions in ammonia-tetrahydrofuran-t-butyl alcohol [49]
    Birch reduction of estradiol 3-methyl ether at 0.12 M concentration [50]
    Birch reduction of the diethyl ketal of estrone 3-methyl ether in ammoma-methylcyclohexane-t-amyl alcohol [51]
    Reduction of 17a-ethynyl-19-nortestosterone to 4,5a-dihydro-17a-ethynyl-19-nortestosterone [52]
    Reductive deacetoxylation of 11-keto-12(?)-Miydroxytigogenin diacetate [53]
    Reductive methylation of the 3-ethylene ketal of pregna-5,16-diene-3,20-dione [54]
    Reactions in ammonia-toluene-tetrahydrofuran solution [54]
2 REDUCTIONS OF STEROIDAL KETONES. Desmond M. S. Wheeler and Margaret M. Wheeler
  I. Introduction [61]
  II. Hydride Reagents [61]
  III. Reaction Conditions [63]
  IV. Mechanism and Stereochemistry of Reductions of Ketones [66]
  V. Unsaturated Ketones [73]
  VI. Stereochemistry of Reductions of Keto Steroids [75]
    Lithium aluminum hydride (LiAlH4) [75]
    Sodium borohydride (NaBH4) [77]
    Lithium tri-(?)-butoxyalurmnum hydride [80]
  VII. Selective Reductions of Polyketo Steroids [81]
    Differential reactivities [81]
    Protecting groups [85]
  VIII. Other Reagents [88]
    Lithium aluminum hydride-aluminum chloride [88]
    Diborane [89]
    Iridium complexes [91]
    Lithium cyanohydridoborate [92]
  IX. Experimental Procedures [92]
    Reductions with sodium borohydride without protecting groups [92]
    Reductions of sodium borohydride with protecting groups [94]
    Reduction with calcium borohydride [97]
    Reduction with lithium aluminum hydride [98]
    Reduction with lithium tri-(?)-butoxyaluminum hydride [99]
    Reduction with diborane [100]
    Reduction with iridium complexes [101]
3 STEROID HYDROGENATION. Robert L. Augustine
  I. Introduction [111]
  II. Factors which Influence Product Stereochemistry [111]
    Hydrogen availability to the catalyst [111]
    The catalyst [113]
    The reaction medium [113]
  III. Olefins [118]
    Isolated and conjugated double bonds [118]
    Carbonyl conjugated double bonds [124]
    Homogeneous catalysis [131]
  IV. Acetylenes [132]
    Selectivity [132]
    Experimental procedure [134]
  V. Ketones [134]
    Selectivity [134]
    Stereochemistry [135]
    Ether formation [136]
    Experimental procedures [136]
  VI. Aromatic Rings [136]
    Selectivity and stereochemistry [136]
    Experimental procedure [138]
  VII. Epoxides [138]
    Selectivity [138]
    Experimental procedures [139]
4 INTRODUCTION OF DEUTERIUM INTO THE STEROID SYSTEM. Laszlo Tokes and Lewis J. Throop
  I. Introduction [145]
  II. Exchange Reactions [146]
    Active hydrogens [147]
    Activated hydrogens in saturated carbonyl compounds [147]
    Activated hydrogens in unsatiirated carbonyl compounds [152]
    Aromatic and benzylic hydrogens [156]
    Aliphatic hydrogens [157]
    Exchange in the spirostan side chain [158]
  III. Reduction of Carbonyl Functions [160]
    Reduction with metal deuteride complexes [162]
    Reduction with alkali metals [165]
    Electrochemical reduction [166]
    Clemmensen reduction [169]
  IV. Reduction of Carbonyl Derivatives [170]
    Desulfurization of mercaptals [171]
    Reduction of tosylhydrazones [173]
    Reduction of oximes [178]
  V. Saturation of Double Bonds [179]
    Heterogeneous catalytic deuteration [179]
    Homogeneous catalytic deuteration [184]
    Reduction with lithium in deuterioammonia [188]
    Deuterioboration [191]
    Reduction with deuteriodiimide [195]
  VI. Displacement Reactions [196]
    Displacement of sulfonate esters [196]
    Displacement of halides [199]
  VII. Ring Opening [204]
    Opening of oxides [204]
    Opening of cyclopropanes [206]
  VIII. Labeling by Partial or Total Syntheses and Derivative Formation [208]
  IX. Preparation of Deuterium-Containing Reagents [212]
    Methanol-OD [212]
    Ethanol-OD [213]
    Isopropanol-OD [213]
    Ammonia-(?) [214]
    Deuteriobromic acid [214]
    Methyl iodide-(?) [214]
    Deuterio-Raney nickel catalyst [215]
5 SELECTIVE OXIDATIONS OF HYDROXY STEROIDS. Gary H. Rasmusson and Glen E Arth
  I. Introduction [222]
  II. Chromium Oxidation [223]
  III. Chromium VI Reagents [227]
    Chromium (?)-acetic acid [227]
    Chromium (?)-acetone [228]
    Chromium trioxide-pyridine complex [229]
    Chromic acid-dimethylformamide [231]
    Two-phase oxidations [232]
  IV. Oxidation with (?)-Halo Compounds [232]
  V. Oppenauer Oxidation [234]
  VI. Dimethyl Sulfoxide Oxidations [237]
  VII. Oxygen [239]
  VIII. Silver Salts [241]
  IX. Lead Tetraacetate [242]
  X. Ruthenium Tetroxide [243]
  XI. Selective Oxidation of Allylic Alcohols [244]
    Manganese dioxide [244]
    Dichlorodicyanobenzoquinone [247]
    Nickel peroxide [248]
  XII. Cupric Acetate [249]
  XIII. Bismuth Trioxide [250]
6 INTRODUCTION OF DOUBLE BONDS INTO THE STEROID SYSTEM. Colin C. Beard
  I. Introduction [265]
    (?), (?)-Unsaturated ketones [266]
    Conjugated and cross-conjugated dienones [266]
    Conjugated and cross-conjugated trienones [266]
    Deconjugated enones [267]
    Simple olefins [267]
    Simple dienes [267]
    Special cases [267]
  II. The Preparation of (?)-Halo Ketones [267]
    Using halogen, kinetic and thermodynarnic products [268]
    The use of enol acetates [271]
    The mechanism and stereochemistry of halogenation, physical methods [273]
    Dihalogenation [276]
    The use of (?)-halo compounds [280]
    The use of other reagents [282]
    The oxidation of halohydrins [283]
    Vinylogous (?)-halo ketones [284]
    The selection of method for bromination [286]
  III. The Dehydrohalogenation of (?)-Halo Ketones [287]
    The use of pyridine bases [287]
    The use of hydrazones [288]
    The use of amide solvents [290]
    The mechanism of dehydrohalogenation [292]
    The choice of method [292]
    Experimental procedures [293]
  IV. The Preparation and Dehydrohalogenation of (?)-Halo Ketals [301]
    Experimental procedures [302]
  V. The Preparation and Elimination of (?)-Substituted Ketones [304]
  VI. The Dehydrogenation of Ketones, Enol Derivatives and Olefms [306]
    The use of chloranil [307]
    The use of dichlorodicyanoquinone (DDQ) [308]
    Experimental procedures [316]
    The use of selenium dioxide [318]
    The use of manganese dioxide [319]
  VII. (?)-Elimination Reactions [320]
    The dehydration of alcohols [320]
    Experimental procedures [328]
    Elimination from sulfonates [328]
    Experimental procedures [331]
    Elimination from halides [332]
    Experimental procedures [333]
    Pyrolytic elimination from esters [334]
    Elimination from nitrogen compounds [337]
  VIII. Reductive Eliminations [338]
    The reduction of vicinal dihalides [338]
    The reduction of halohydrins, halohydrin esters and epoxides [341]
    Experimental procedures [343]
    The reduction of vicinal diol esters [344]
  IX. The Reduction of (?), (?)-Unsaturated Ketones [345]
    Experimental procedures [347]
  X. The Reduction of a-Substituted Ketones [348]
  XI. The Reduction of Keto Derivatives [351]
    The reduction of ketones via hydrazone derivatives [351]
    Experimental procedures [354]
    The reduction of enol derivatives [355]
    The reduction of thioketals [356]
    Experimental procedures [356]
  XII. The Cleavage of Cyclopropanes [357]
  XIII. The Nonreductive Cleavage of Oxides [358]
  XIV. The Isomerization of Olefms and Deconjugation of Enones [360]
    Experimental procedures [363]
7 PROTECTION OF CARBONYL AND HYDROXYL GROUPS. R. Gardi and A. Ercoli
  I. General Discussion [375]
    Factors governing choice of protecting groups [375]
    Factors governing selectivity in formation of protecting groups [375]
    Factors governing selectivity in removal of protecting groups [382]
    Stability [385]
  II. Applications [388]
    Protection of carbonyl groups [388]
    Protection of hydroxyl groups [402]
  III. Experimental Procedures [406]
    Protection of ketones [406]
    Protection of hydroxyl groups [413]
8 INTRODUCTION OF FLUORINE INTO THE STEROID SYSTEM. Josef Fried and N. A. Abraham
  I. Introduction [423]
  II. Vicinal Fluorohydrins [425]
    Choice of reagents [425]
    Mechanism and stereochemistry [432]
    Experimental procedures [433]
  III. Monofluorides [436]
    Choice of reagents [436]
    Experimental procedures [446]
  IV. Vicinal Difluorides [451]
    Choice of reagents [451]
    Experimental procedures [453]
  V. Vicinal Fluorohalides [454]
    Choice of reagents [454]
    Mechanism and stereochemistry [457]
    Experimental procedures [458]
  VI. Geminal (?)- and trifluorides [459]
    Choice of reagents [459]
    Experimental procedures [471]
  VII. 2-Fluoro Ketones and Vinylogous Fluoro Ketones [474]
    Choice of reagents [474]
    Experimental procedures [484]
    Experimental Procedures Index [495]
    Subject Index [499]
CONTENTS TO VOLUME II
9 SYNTHESIS OF OXIRANES, AZIRIDINES AND EPISULFIDES. Gary J. Matthews and Alfred Hassner
10 SELECTIVE INTRODUCTION OF ALKYL AND METHYLENE GROUPS INTO THE STEROID SYSTEM. Henry Laurent and Rudolf Wiechert
11 SYNTHESIS AND DEGRADATION OF THE PREGNANE SIDE-CHAIN. Eugene P. Oliveto
12 SELECTIVE FUNCTIONALIZATION OF THE ANGULAR METHYL GROUP AND FURTHER TRANSFORMATION TO 19-NORSTEROIDS. Karl Heusler and Jaroslav Kalvoda
13 PHOTOCHEMICAL REARRANGEMENTS AND CYCLOADDITIONS. Kurt Schaffner
14 RING EXPANSION AND SIMULTANEOUS RING CONTRACTION—RING EXPANSION. George A. Boswell, Jr.
15 RING CONTRACTIONS. Richard M. Scribner
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