Decarboxylation-promoted Pd-catalyzed asymmetric propargylic [3 + 2] annulation for the enantioselective construction of a quaternary stereocenter in 2,3-dihydrofurans†,Organic & Biomolecular Chemistry

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Decarboxylation-promoted Pd-catalyzed asymmetric propargylic [3 + 2] annulation for the enantioselective construction of a quaternary stereocenter in 2,3-dihydrofurans†
Organic & Biomolecular Chemistry ( IF 2.9 ) Pub Date : 2018-01-02 00:00:00 , DOI: 10.1039/c7ob02778h
Kun Li _{1,

2,

3,

4,

5} , Fu-Lin Zhu _{4,

5,

6,

7} , Zhen-Ting Liu _{4,

5,

6,

7} , Jing Tong _{1,

2,

3,

4} , Xiang-Ping Hu _{4,

5,

6,

7}

Affiliation

The enantioselective construction of a quaternary stereocenter in 2,3-dihydrofuran frameworks has been realized via the palladium-catalyzed asymmetric [3 + 2] cycloaddition of tertiary propargylic carbonates with β-ketoesters enabled by a chiral ferrocene/benzimidazole-based bidentate P,N-ligand. The reaction was significantly promoted by loss of CO₂ to irreversibly form π-propargylpalladium or allenylpalladium intermediates. This protocol features a good tolerance of functional groups in both tertiary propargylic carbonates and β-ketoesters, thereby delivering a variety of highly functionalized chiral 2,3-dihydrofurans bearing a quaternary stereocenter at the 2-position and an exocyclic double bond at the 3-position in good chemical yields and high enantioselectivities (up to 98% ee).

中文翻译：

脱羧促进的Pd催化的不对称炔丙基[3 + 2]环化反应，用于2,3-二氢呋喃中四元立体中心的对映选择性构建†

季立构的2,3-二氢呋喃的框架对映结构已经实现通过钯催化的不对称[3 + 2]环加成叔炔碳酸酯与β酮酯能够通过手性二茂铁/苯并咪唑为基础的二齿P，N -配体。CO ₂的损失显着促进了反应不可逆地形成π-炔丙基钯或烯丙基钯中间体。该方案的特点是对叔炔丙基碳酸酯和β-酮酸酯中的官能团具有良好的耐受性，从而提供了各种高度官能化的手性2,3-二氢呋喃，其2-位带有一个立体立体中心，而3-位带有一个环外双键。具有良好的化学收率和高对映选择性（高达98％ee）的位置。

更新日期：2018-01-02

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