Organic Reactions in Steroid Chemistry. Volume 2

Автор(ы):Fried J.
06.10.2007
Год изд.:1972
Описание: The aim of this book to make a critical review both theoretical and experimental aspects of some of the most important and synthetically useful transformations in steroid chemistry. The editors consider the recommended experimental procedures to be particularly valuable because of the authors substantial personal research experience and frequently pioneering work with the reactions under discussion. It is hoped that these volumes will be useful not only to the chemist who wishes to carry out synthesis in the steroid field, but also to the broader group of organic chemists who are interested in carrying out selective and stereo-chemically defined reactions, as well as protective chemistry on extraneous functional groups, during a road range of synthetic applications.
Оглавление:
Organic Reactions in Steroid Chemistry. Volume 2 — обложка книги.
9 SYNTHESIS OF OXIRANES, AZIRIDINES AND EPISULFIDES. Gary J. Matthews and Alfred Hassner
  I. General Introduction [1]
  II. Oxiranes [2]
    Introduction [2]
    Peracid epoxidation [2]
    Alkaline hydrogen peroxide epoxidation [10]
    Conversion of an oxirane into its stereoisomer [14]
    Epoxide formation via halohydrins [15]
    Spectra [18]
    Experimental procedures [19]
  III. Aziridines [22]
    Introduction [22]
    Iodine isocyanate addition to olefins [22]
    Halogen azide addition to olefins [24]
    Via epoxides and (?)-mesyloxy azides [27]
    By addition of alkoxyamines [29]
    Addition of cyanogen azide and "nitrenoid" species to olefins [30]
    Miscellaneous [30]
    Spectra [31]
    Experimental procedures [31]
  IV. Thiiranes [37]
    Introduction [37]
    By thiocyanate opening of epoxides [37]
    From a-bromo ketones [42]
    Spectra [42]
    Experimental procedures [42]
10 SELECTIVE INTRODUCTION OF ALKYL AND METHYLENE GROUPS INTO THE STEROID SYSTEM. Henry Laurent and Rudolf Wiechert
  I. Organometallic Additions to Ketones, Conjugated Ketones and Epoxides [53]
    Introduction [53]
    Organometallic addition to ketones [56]
    Grignard additions to unsaturated ketones [75]
    Organometallic addition to epoxides [82]
  II. Alkylation via Enolate Anions [86]
    Introduction [86]
    Direct alkylation [87]
    Alkylation of Formyl ketones [93]
    Methylation of (?)-oxalyl ketones [95]
    Reductive alkylation [97]
  III. Addition of Diazomethane to Enones [100]
    Introduction [100]
    Discussion [102]
  IV. Simmons-Smith Reaction [107]
    Introduction [107]
    Discussion [108]
  V. Addition of Dimethyloxosulfonium Methylide to Enones [113]
    Introduction [113]
    Discussion [115]
11 SYNTHESIS AND DEGRADATION OF THE PREGNANE SIDE-CHAIN. Eugene P. Oliveto
  I. Introduction [127]
  II. The Conversion of Antrostanes to Pregnanes [129]
    The Wittig reaction [129]
    Via 17-cyanohydrins [132]
    The addition of acetylenes [136]
    The Reformatsky reaction [139]
  III. The Conversion of Pregnanes to Androstanes [140]
    The Beckmann rearrangement [140]
    The Schmidt rearrangement [144]
    Microbiological degradation of pregnanes to androstanes [146]
    The cleavage (?)-oxygenated pregnanes [147]
    The Ваеуег-Villiger reaction [151]
    Nitrite degradation [154]
    Nitrite photolysis [154]
    Manganese dioxide degradation [156]
    Degradation via 17-hydroperoxides [156]
    Ozonolysis of A17(20)-pregnenes [158]
    Fragmentation of 16-oxygenated pregnanes [162]
  IV. Side-Chain Oxygenation of Pregnanes [162]
    17-Mono-oxygenated pregnanes [162]
    20-Mono-oxygenated pregnanes [165]
    21-Mono-oxygenated pregnanes [176]
    17,20-Bis-oxygenated pregnanes [183]
    20,21-Bis-oxygenated pregnanes [201]
    17,20,21-Tris-oxygenated pregnanes [217]
12 SELECTIVE FUNCTIONALIZATION OF THE ANGULAR METHYL GROUP AND FURTHER TRANSFORMATION TO 19-NORSTEROIDS. Karl Heusler and Jaroslav Kalvoda
  I. Introduction [237]
  II. Functionalization of the Angular Methyl Groups [237]
    General principles of substitution [237]
    Lead tetraacetate oxidations [240]
    Hypohalite reactions [246]
    Photolysis of nitrites (Barton reaction) [253]
    N-Chloroamine reactions (Hoffmann-Loffler reaction) [257]
    Ketone irradiations [260]
    Summary [264]
  III. Preparation of 19-Norsteroids from 19-Substituted Steroids [264]
    Transformations of 6(?), 19-ethers [264]
    Transformation of 19-oximino derivatives [268]
    Removal of the C-10 substituent [272]
    Summary and procedures for 19-norsteroids [278]
13 PHOTOCHEMICAL REARRANGEMENTS AND CYCLO-ADDITIONS. Kurt Schaffner
  I. Introduction [288]
  II. Transformations of Nonconjugated Ketones [292]
    (?)-Cleavage [296]
    Oxacarbene formation [307]
    Cleavage of bonds attaching atoms or groups to the (?)-carbon of ketones [307]
    Cyclic (?)-diazoketones: Ring contraction in photolytic Wolff rearrangements [316]
    Autooxidation of ketones [316]
  III. Transformations of Conjugated Cyclohexenones [317]
    The cyclohex-2-enone -> bicyclo[3.1.0]hexan-2-one rearrangement [318]
    Cyclohex-2-enones: Cleavage of exocyclic (?),(?)-bonds and (?)->(?)-bonding to (?),(?)-double bonds [323]
    Rearrangements of cross-conjugated cyclohexadienones and their photoisomers [330]
  IV. Rearrangements of Enol Esters and Enol Lactones [339]
  V. Cycloadditions to Conjugated Enones [343]
14 RING EXPANSION AND SIMULTANEOUS RING CONTRACTION—RING EXPANSION. George A. Boswell, Jr.
  I. Introduction [354]
  II. Ring A Expansion: A-Homosteroids [355]
    Saturated A-homo ketones [355]
    Unsaturated A-homosteroids [361]
    Ring A tropones [367]
    Summary [373]
  III. B-Homosteroids [374]
    Saturated B-homo ketones and hydrocarbons [374]
    Unsaturated B-homo ketones [378]
    B-Homo-19-norsteroids [379]
    Summary [382]
  IV. D-Homosteroids [382]
    Ring D homoannulation of 17-hydroxy-20-ketopregnane erivatives [382]
    Tiffeneau ring enlargement of 17-keto steroids [386]
    Summary [389]
  V. 10(5->6(?)H)Abeosteroids (A-Homo-B-Norsteroids) [389]
    Solvolysis of 5a,6a-epoxy-6-methyl steroids [389]
    Pinacol rearrangement of 5a-hydroxy-6a-tosylates [392]
    Summary [394]
  VI. 10(5 -> 4),(?)steroids (A-Homo-B-Homosteroids) [395]
    From (?)-keto steroids [395]
    By photolysis [396]
    By solvolysis of (?)-hydroxy-(?)-tosyloxy steroids [398]
    Summary [400]
  VII. 14(13->12aH)yl6eosteroids (C-Nor-D-Homo Steroids) [400]
    By solvolysis of 12(?)-methylsulfonyloxy steroids [400]
    By fragmentation-rearrangement of 12-tosylhydrazones [402]
15 RING CONTRACTIONS. Richard M. Scribner
  I. Introduction [408]
  II. A-Norsteroids [408]
    Pyrolysis of 2,3-seco-2,3-dicarboxylic acid anhydrides [408]
    Pyrolysis of (?)-2,3-seco-2,3-dicarboxylic acid anhydrides [410]
    Reaction of enamines of 3-ketones with cyanogen azide [412]
    Retropinacol rearrangement of 4,4-dimethyl-3(?)-ols [416]
    Benzilic acid rearrangement of (?)-ring (?)-diketones [418]
    Oxidative rearrangements of (?)-ring (?)-diketones by manganese dioxide [426]
    Photochemical rearrangements [428]
  III. (?)-Norsteroids [429]
    Chromium trioxide oxidation of (?)-steroids [429]
    Ozonization of (?)-steroids [431]
    Baeyer-Villiger oxidation of 5-hydroxy-6-keto steroids [433]
  IV. (?)-Norsteroids [435]
    Benzilic rearrangements [435]
    Rearrangement of epoxides [438]
  V. (?)-Norsteroids [439]
    Photolysis of (?)-diazoketones [439]
    Experimental Procedures Index [449]
    Subject Index [455]
CONTENTS TO VOLUME I
1 REDUCTIONS OF STEROIDS BY METAL-AMMONIA SOLUTIONS. Hugh L. Dryden, Jr.
2 REDUCTIONS OF STEROIDAL KETONES. Desmond M. S. Wheeler and Margaret M. Wheeler
3 STEROID HYDROGENATION. Robert L. Augustine
4 INTRODUCTION OF DEUTERIUM INTO THE STEROID SYSTEM. Laszlo Tokes and Lewis J. Throop
5 SELECTIVE OXIDATIONS OF HYDROXY STEROIDS. Gary H. Rasmusson and Glen E. Arth
6 INTRODUCTION OF DOUBLE BONDS INTO THE STEROID SYSTEM. Colin C. Beard
7 PROTECTION OF CARBONYL AND HYDROXYL GROUPS. R. Gardi and A. Ercoli
8 INTRODUCTION OF FLUORINE INTO THE STEROID SYSTEM. Josef Fried and N. A. Abraham
Формат: djvu
Размер:6165361 байт
Язык:ENG
Рейтинг: 141 Рейтинг
Открыть: