Evolution of the Dearomative Functionalization of Activated Quinolines and Isoquinolines: Expansion of the Electrophile Scope.
Evolution of the Dearomative Functionalization of Activated Quinolines and Isoquinolines: Expansion of the Electrophile Scope.
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DOI：
10.1002/anie.202204682
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发表时间：
2022-07-04
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影响因子：
--
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本文中，我们公开了用于喹啉鎓盐和异喹啉鎓盐的还原官能化的温和方案。该反应在无过渡金属的条件下以及在具有非常低的催化剂负载（0.01摩尔%）的铑催化下进行，并使用廉价的甲酸作为末端还原剂。 广泛的亲电体，包括烯酮、酰亚胺、不饱和酯和砜、β-硝基苯乙烯和醛被原位形成的烯胺物质拦截，形成多种取代的四氢（异）喹啉。亲电体分别在喹啉和异喹啉的C-3和C-4位置并入，提供了在亲电或亲核芳族取代中不受欢迎的取代模式。最后，这种反应性被用来促进三种类型的成环反应，产生复杂的多环产品的正式[3+3]或[4+2]环加成。在不含过渡金属的条件下或在具有非常低的催化剂负载量的铑催化下，用甲酸作为末端还原剂的喹啉鎓盐和异喹啉鎓盐的还原官能化是可能的。广泛的亲电体，包括烯酮、酰亚胺、不饱和酯和砜、β-硝基苯乙烯和醛，被原位形成的烯胺物质拦截以生成取代的四氢（异）喹啉。
Herein we disclose a mild protocol for the reductive functionalisation of quinolinium and isoquinolinium salts. The reaction proceeds under transition‐metal‐free conditions as well as under rhodium catalysis with very low catalyst loadings (0.01 mol %) and uses inexpensive formic acid as the terminal reductant. A wide range of electrophiles, including enones, imides, unsaturated esters and sulfones, β‐nitro styrenes and aldehydes are intercepted by the in situ formed enamine species forming a large variety of substituted tetrahydro(iso)quinolines. Electrophiles are incorporated at the C‐3 and C‐4 position for quinolines and isoquinolines respectively, providing access to substitution patterns which are not favoured in electrophilic or nucleophilic aromatic substitution. Finally, this reactivity was exploited to facilitate three types of annulation reactions, giving rise to complex polycyclic products of a formal [3+3] or [4+2] cycloaddition. Reductive functionalisation of quinolinium and isoquinolinium salts with formic acid as the terminal reductant was possible under transition‐metal‐free conditions or rhodium catalysis with very low catalyst loadings. A wide range of electrophiles, including enones, imides, unsaturated esters and sulfones, β‐nitrostyrenes and aldehydes, were intercepted by the enamine species formed in situ to generate substituted tetrahydro(iso)quinolines.
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影响因子：
15
作者：
Gribble MW Jr;Guo S;Buchwald SL
通讯作者：
Buchwald SL
影响因子：
2.7
作者：
Dong, Linru;Ma, Xinyue;Wang, Dong
通讯作者：
Wang, Dong
影响因子：
15
作者：
DANISHEFSKY, S;CAIN, P;NAGEL, A
通讯作者：
NAGEL, A
影响因子：
3.6
作者：
CHEN, TK;BRADSHER, CK
通讯作者：
BRADSHER, CK
影响因子：
1.8
作者：
DEKONING, AJ;BUDZELAAR, PHM;BOERSMA, J
通讯作者：
BOERSMA, J