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Visible-Light-Accelerated Pd-Catalyzed Cascade Addition/Cyclization of Arylboronic Acids to γ- and β-Ketodinitriles for the Construction of 3-Cyanopyridines and 3-Cyanopyrrole Analogues.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-09-09 , DOI: 10.1021/acs.joc.0c01703 Amitava Rakshit 1 , Prashant Kumar 1 , Tipu Alam 1 , Hirendranath Dhara 1 , Bhisma K Patel 1
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2020-09-09 , DOI: 10.1021/acs.joc.0c01703 Amitava Rakshit 1 , Prashant Kumar 1 , Tipu Alam 1 , Hirendranath Dhara 1 , Bhisma K Patel 1
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The one-pot synthetic strategies for 2,4,6-triarylnicotinonitriles and 2,5-diaryl-1H-pyrrole-3-carbonitriles have been accomplished via a Pd-catalyzed coupling of arylboronic acid with 2-(3-oxo-1,3-diarylpropyl)malononitrile and 2-(2-oxo-2-arylethyl)malononitrile, respectively, under mild reaction conditions, followed by intramolecular cyclization of an intermediate formed after the regeneration of the catalyst under acidic reaction conditions. The cascade reactions proceed in 1,2-dichloroethane solvent under visible-light irradiation, and the active catalyst is generated in situ in the presence of catalytic amounts of Pd(OAc)2 and 2,2′-bipyridine. The active Pd catalyst undergoes photoexcitation by the virtue of metal-to-ligand charge transfer (MLCT), and subsequent redox trans-metalation occurs with arylboronic acid, thus obviating the necessity of any exogenous photosensitizer. The targeted products, composed of a new C–C, a C–N, a C═N, and two new C═C bonds, were isolated in good yields.
中文翻译：
可见光加速的Pd催化的芳基硼酸级联加成/环化反应生成γ-和β-乙酮腈，用于构建3-氰基吡啶和3-氰基吡咯类似物。
一锅合成策略的2,4,6-三芳基烟腈和2,5-二芳基-1 H-吡咯-3-腈是通过Pd催化的芳基硼酸与2-（3-oxo-1）偶联而完成的，在温和的反应条件下，分别将3-3-二芳基丙基）丙二腈和2-（2-氧代-2-芳基乙基）丙二腈，然后在酸性反应条件下，将催化剂再生后形成的中间体进行分子内环化。级联反应在1,2-二氯乙烷溶剂中在可见光照射下进行，并且在催化量的Pd（OAc）2存在下原位生成活性催化剂和2,2'-联吡啶。活性Pd催化剂借助金属到配体的电荷转移（MLCT）进行光激发，随后芳基硼酸发生氧化还原反金属化，因此无需任何外源光敏剂。以高收率分离出由新的C–C，C–N，C aN和两个新的C═C键组成的目标产物。
更新日期：2020-10-02
中文翻译：
可见光加速的Pd催化的芳基硼酸级联加成/环化反应生成γ-和β-乙酮腈，用于构建3-氰基吡啶和3-氰基吡咯类似物。
一锅合成策略的2,4,6-三芳基烟腈和2,5-二芳基-1 H-吡咯-3-腈是通过Pd催化的芳基硼酸与2-（3-oxo-1）偶联而完成的，在温和的反应条件下，分别将3-3-二芳基丙基）丙二腈和2-（2-氧代-2-芳基乙基）丙二腈，然后在酸性反应条件下，将催化剂再生后形成的中间体进行分子内环化。级联反应在1,2-二氯乙烷溶剂中在可见光照射下进行，并且在催化量的Pd（OAc）2存在下原位生成活性催化剂和2,2'-联吡啶。活性Pd催化剂借助金属到配体的电荷转移（MLCT）进行光激发，随后芳基硼酸发生氧化还原反金属化，因此无需任何外源光敏剂。以高收率分离出由新的C–C，C–N，C aN和两个新的C═C键组成的目标产物。
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