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  • 2 2 photocycloaddition studies on complex Tetronic Acid esters related to the synthesis of cembranoid diterpenes
    ChemInform, 2015
    Co-Authors: Roland Weixler, Thorsten Bach
    Abstract:

    The synthesis of twelve differently substituted tetronates such as (I), (III), and (V) is described.

  • 2 2 photocycloaddition studies on complex Tetronic Acid esters related to the synthesis of cembranoid diterpenes
    Synthesis, 2014
    Co-Authors: Roland Weixler, Thorsten Bach
    Abstract:

    Twelve different Tetronic Acid esters bearing two potentially reactive olefinic groups were prepared and subjected to [2+2] photocycloaddition reactions by irradiation at λ = 254 nm in tert-butanol (5 mM). The diastereoselectivity and regioselectivity of the reaction was studied with regard to the synthesis of cembranoid diterpenes. When the Tetronic Acid core carried an alk-3-enyl substituent in the γ-position and an alk-3-enyloxy substituent in the β-position, the undesired γ-products prevailed and were formed in 48–81% yield. Altering the γ-alk-3-enyl substituent into an alk-3-ynyl or alk-2-ynyl substituent, resulted in formation of the desired β-photocycloaddition products. The latter products were obtained in yields of 56–88%, with two out of three products exhibiting very high regio- and diastereoselectivity.

  • conformationally constrained β amino Acid derivatives by intramolecular 2 2 photocycloaddition of a Tetronic Acid amide and subsequent lactone ring opening
    Journal of Organic Chemistry, 2005
    Co-Authors: Birte Basler, Oliver Schuster, Thorsten Bach
    Abstract:

    The N-Boc-protected N-3-alkenylTetronic Acid amides 9 and 12 were prepared from Tetronic Acid bromide (7) and the corresponding amines 6 and 10 by nucleophilic substitution and subsequent acylation in 71% and 39% overall yield. They underwent an intramolecular [2 + 2]-photocycloaddition upon direct irradiation (λ = 254 nm) to yield diastereoselectively the strained lactones 15 (76%) and 16 (91%) with a 2-azabicyclo[3.2.0]heptane core. In attempts to defunctionalize the 1-hydroxymethyl substituent of the 2-azabicyclo[3.2.0]heptane skeleton, lactone 15 was converted into mesylate 18 (74% overall yield). Intermolecular substitution reactions on this mesylate, however, proceeded sluggishly or failed completely. Lactone 15 could be opened reductively (Dibal-H) or by substitution with benzylamine to the N-Boc-protected 2-azabicyclo[3.2.0]heptanes 21 (71%) and 22 (81%). Conformationally constrained β-amino Acid derivatives were obtained by quantitative N-Boc deprotection of photocycloaddition product 15, followe...

Lixin Wang - One of the best experts on this subject based on the ideXlab platform.

Jing Zhou - One of the best experts on this subject based on the ideXlab platform.