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  • 1985-1989  (2)
  • Synthetic methods  (2)
  • 1
    Electronic Resource
    Electronic Resource
    [3+2] Cycloaddition Approaches to Five-Membered Rings via Trimethylenemethane and Its Equivalents [New Synthetic Methods (55)] (1986)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 25 (1986), S. 1-20 
    Details
    ISSN: 0570-0833
    Keywords: Cycloaddition ; Trimethylenemethane ; Synthetic methods ; Cyclopentanes ; Heterocycles ; Natural products ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The power of cycloadditions for ring formation derives from the potential for chemo-, regio-, diastereo-, and enantioselectivity. Trimethylenemethane (TMM) and its equivalents offer the possibility of extending such benefits to the synthesis of five-membered rings. Three types of conjunctive reagents appear to be promising candidates: (1) selected 4-alky-lidene-4,5-dihydro-3H-pyrazoles, (2) 2-[(trimethylsilyl)methyl]allyl esters and halides, and (3) alkylidenecyclopropanes. Thermal reactions, especially intramolecular ones, effect the cycloaddition of the pyrazoles to olefins-especially electron-poor olefins. The latter two precursors require a catalyst, notably a palladium complex, to unlock the synthetic potential. With the 2-[(trimethylsilyl)methyl]allyl esters, a general chemo-, regio-, and diastereoselective cycloaddition with typical Diels-Alder dienophiles forms methylenecyclopentanes in both inter- and intramolecular fashion. A tin analogue allows extension of this cycloaddition to aldehydes, and, in a related sequence, to ketones and imines to form 3-methylenete-trahydrofurans and 3-methylenepyrrolidines with excellent diastereoselectivity. The 2-[(tri-methylsilyl)methyl]allyl esters also serve to effect net methylenecyclopentane annulation to cyclic enols. Such adducts can further undergo three-carbon intercalation or combined ring contraction-spiroannulation simply by the use of either a nucleophilic or electrophilic trigger. Alkylidenecyclopropanes undergo cycloadditions to both electron-rich and electron-poor olefins when stimulated by metal catalysts, especially palladium. A complementary regiochemistry to the approach based upon silicon conjunctive reagents is observed. The availability of these cycloadditions provides new strategies for the synthesis of natural products.
    Additional Material: 2 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.198600013
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    Paper (German National Licenses)
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  • 2
    Electronic Resource
    Electronic Resource
    Cyclizations via Palladium-Catalyzed Allylic Alkylations [New Synthetic Methods (79)] (1989)
    Weinheim : Wiley-Blackwell
    Angewandte Chemie International Edition in English 28 (1989), S. 1173-1192 
    Details
    ISSN: 0570-0833
    Keywords: Cyclization ; Allylic alkylation ; Alkylation ; Synthetic methods ; Palladium ; Catalysis ; C-C coupling ; Chemistry ; General Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The history of ring systems in organic chemistry parallels their synthetic accessibility. Transition-metal-catalyzed cyclizations offer a new opportunity to create carbo- and heterocyclic compounds with great facility. Among these methods, allylic alkylations catalyzed by palladium have proven unusually productive because of the extraordinary chemo-, regio-, and diastereoselectivity and the continuing possibility for the development of enantioselectivity. The rules for ring closure differ from those for non-transition-metal-catalyzed reactions. A major benefit is the ability to generate medium (eight-, nine-, ten-, and eleven-membered) and large rings in preference to normal (five-, six- and seven-membered) rings. With the appropriate substrate, efficient macrocyclizations are possible under conditions of normal concentrations. A second major benefit derives from the complementary stereochemistry of the metalcatalyzed substitution (net retention of configuration) compared to non-metal-catalyzed reactions (inversion of configuration). Further, the requirement for the substrate to conform to the transition-metal template may impose a stereochemical preference in the intermediate that ultimately translates into the thermodynamically less stable organic product regardless of the stereochemistry of the starting material. While more work has focused on carbocyclic synthesis, the possibilities for heterocyclic synthesis are just beginning to be tapped. In addition to forming heterocycles by C—C bond formation, use of a heteroatom as a nucleophile has already proven effective for oxygen and nitrogen, with other nucleophiles awaiting investigation. New dimensions for cyclization via allylic alkylation arise by generating the requisite π-allylpalladium intermediates by methods other than palladium(0)-initiated allylic ionizations. In addition, metals other than palladium will clearly expand the possibilities, but as yet remain untapped.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/anie.198911731
    Library Location Call Number Volume/Issue/Year Availability
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    Paper (German National Licenses)
    Fulltext
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