Click Organocatalysis: Acceleration of Azide-Alkyne Cycloadditions with Mutually Orthogonal Click Reactions.
Click Organocatalysis: Acceleration of Azide-Alkyne Cycloadditions with Mutually Orthogonal Click Reactions.
复制标题
点击有机催化：通过相互正交的点击反应加速叠氮-炔环加成。
DOI：
10.1021/acs.joc.3c02182
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发表时间：
2024
期刊：
影响因子：
--
通讯作者：
Raines,RonaldT
中科院分区：
文献类型：
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作者：
Levandowski,BrianJ;Graham,BrianJ;Houk,KN;Raines,RonaldT
“点击有机催化”使用相互正交的点击反应来有机催化点击反应。我们报道了一种异苯并呋喃有机催化剂的发展，它可以提高叠氮化物-炔环加成反应的速率和区域选择性。有机催化循环由以下组成：（1）炔与二芳基异苯并呋喃的Diels-桤木反应形成苯并氧杂降冰片二烯，（2）与叠氮化物的1，3-偶极环加成形成4，5-二氢-1，2，3-三唑，和（3）释放三唑产物并再生二芳基异苯并呋喃有机催化剂的逆Diels-桤木反应。计算设计了二芳基异苯并呋喃有机催化剂，用于催化全氟苯基叠氮和丙炔酸甲酯反应，选择性地形成1，4-三唑产物。用4-叠氮基-2，3，5，6-四氟苯甲酸甲酯和丙炔酸甲酯对所设计的有机催化剂进行了实验验证。
“Click organocatalysis” uses mutually orthogonal click reactions to organocatalyze a click reaction. We report the development of an isobenzofuran organocatalyst that increases the rate and regioselectivity of an azide–alkyne cycloaddition. The organocatalytic cycle consists of (1) a Diels–Alder reaction of an alkyne with a diarylisobenzofuran to form a benzooxanorbornadiene, (2) a 1,3-dipolar cycloaddition with an azide to form a 4,5-dihydro-1,2,3-triazole, and (3) a retro-Diels–Alder reaction that releases the triazole product and regenerates the diarylisobenzofuran organocatalyst. The diarylisobenzofuran organocatalyst was computationally designed to catalyze the reaction of perfluorophenyl azide and methyl propiolate to selectively form a 1,4-triazole product. Experimental validation of the designed organocatalyst was obtained with methyl 4-azido-2,3,5,6-tetrafluorobenzoate and methyl propiolate.