Strain‐Induced Nucleophilic Ring Opening of Donor–Acceptor Cyclopropenes for Synthesis of Monosubstituted Succinic Acid Derivatives
Strain‐Induced Nucleophilic Ring Opening of Donor–Acceptor Cyclopropenes for Synthesis of Monosubstituted Succinic Acid Derivatives
复制标题
应变诱导供体-受体环丙烯亲核开环用于合成单取代琥珀酸衍生物
DOI：
10.1002/chem.202003427
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Doyle, Michael P.
中科院分区：
文献类型：
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作者：
Marichev, Kostiantyn O.;Wang, Kan;Greco, Nicole;Dong, Kuiyong;Chen, Jinzhou;Lei, Jinping;Doyle, Michael P.
由烯醇重氮化合物原位生成的 1,2,3-三取代供体-受体环丙烯 (DACP) 与亲核试剂反应，以高产率形成 α-取代琥珀酸衍生物。当催化量的 4-二甲基氨基吡啶 (DMAP) 促进时，初始羧酸二铑 (II) 催化快速将烯醇重氮乙酸酯或乙酰胺转化为 DACP，DACP 与胺、苯胺、醇和硫醇进行无催化剂 Favorskii 开环。该方法可以轻松获得单取代琥珀酸的混合酯和酰胺，包括天然存在的化合物的衍生物。它还以高产率提供二酰肼、二异羟肟酸和二酰胺衍生物，以及 α-取代的四氢哒嗪-3,6-二酮。生成光学富集的 DACP 的尝试并不成功，因为它们具有用手性二铑催化剂形成的 RandS 构型的群体非常相似，并且对映体控制的损失可能源自 DACP 成环步骤，该步骤与其中间体金属卡宾是可逆的。
1,2,3‐Trisubstituted donor–acceptor cyclopropenes (DACPs) generated in situ from enoldiazo compounds react with nucleophiles to form α‐substituted succinic acid derivatives in high yields. Initial dirhodium(II) carboxylate catalysis rapidly converts enoldiazo‐acetates or ‐acetamides to DACPs that undergo catalyst‐free Favorskii ring opening with amines, and also with anilines, alcohols, and thiols, when facilitated by catalytic amounts of 4‐dimethylaminopyridine (DMAP). This methodology provides easy access to mixed esters and amides of monosubstituted succinic acids, including derivatives of naturally occurring compounds. It also affords dihydrazide, dihydroxamic acid, and diamide derivatives, as well as α‐substituted tetrahydropyridazine‐3,6‐diones in high yields. Attempts to generate optically enriched DACPs were not successful because their populations having theRandSconfigurations formed with a chiral dirhodium catalyst are quite similar, and the loss of enantiocontrol likely originates from the DACP ring forming step which is reversible with its intermediate metal carbene.