Switch of Selectivity in the Synthesis of α‐Methylene‐γ‐Lactones: Palladium‐Catalyzed Intermolecular Carboesterification of Alkenes with Alkynes

Изменение селективности в синтезе α‑метилен‑γ‑лактонов: палладий‑катализируемая межмолекулярная карбоэфирофикация алкенов алкинами
Huanfeng Jiang, Qian Wang, Xiaohang Liu, Liangbin Huang
2012-04-23

C–O bond formationPdII-catalyzed carboesterificationintermolecular alkyne–alkene couplingstereoselectivity control (substrate and temperature)α-methylene-γ-lactone synthesis
Three in one: A highly efficient and mild PdII-catalyzed carboesterification of alkenes with carboxylic alkyne derivatives proceeds through a domino-type alkyne–alkene coupling/CO-bond formation (see scheme). The stereoselectivity is controlled by the choice of substrates and temperature. The reaction provides a convenient method for the construction of naturally occurring biologically active compounds with α-methylene-γ-lactone skeletons. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
1
A Pd(II)-catalyzed intermolecular carboesterification of alkenes with carboxylic alkyne derivatives was developed.
2
Stereoselectivity of the transformation can be switched/controlled by choice of substrates and reaction temperature.
3
The method is highly efficient and operates under mild conditions.
4
The protocol provides a convenient route to construct naturally occurring biologically active compounds bearing α-methylene-γ-lactone skeletons.
5
The reaction proceeds via a domino-type alkyne–alkene coupling followed by C–O bond formation to give α-methylene-γ-lactones.

Pd(II)-catalyzed intermolecular carboesterification reaction of alkenes with carboxylic alkyne derivatives producing α-methylene-γ-lactones

Switch of stereoselectivity (control of stereoselectivity) in the domino alkyne–alkene coupling/C–O bond-forming process as a function of substrate choice and temperature leading to selective formation of α-methylene-γ-lactone skeletons

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2012-04-23
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Huanfeng Jiang
Qian Wang
Xiaohang Liu
Liangbin Huang
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