Polycyclic Ring Formation Using Bis-diazolactams for Cascade Stitching
Polycyclic Ring Formation Using Bis-diazolactams for Cascade Stitching
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DOI：
10.1021/acs.joc.6b02663
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发表时间：
2017-01-06
影响因子：
3.6
通讯作者：
Padwa, Albert
中科院分区：
文献类型：
--
作者：
Bonderoff, Sara A.;Padwa, Albert
研究了铑（Ⅱ）催化下3-重氮-1-（乙基2-重氮丙二酰）-吲哚啉-2-酮（3-diazo-1-（ethyl 2-diazomalonyl）-indolin-2-one）对同一分子中给体/受体（D/A）和受体/受体（A/A）重氮基团的化学选择性反应。衍生自D/A重氮基团的金属类卡宾优先形成，并经历选择性CH、NH和OH插入反应、环丙烷化、环丙烯化、硫叶立德形成/2，3-σ迁移重排以及氮叶立德形成，然后氮杂环丁烷扩环。初始反应可以与随后的串联级联序列配对，所述串联级联序列涉及分子内或分子间意义上的偶极形成/环加成，以在一锅中产生多环N-杂环，在单个操作中形成多达三个新的环。在分子内环加成反应中观察到良好的非对映选择性，产生5至7元环。
The chemoselective reaction of donor/acceptor (D/A) and acceptor/acceptor (A/A) diazo moieties in the same molecule was examined using 3-diazo-1-(ethyl 2-diazomalony1)-indolin-2-one under rhodium(II) catalysis. The metallo carbenoid derived from the D/A diazo group is preferentially formed and undergoes selective CH, NH, and OH insertion reactions, cyclopropanation, cyclopropenation, sulfur ylide formation/2,3-sigmatropic rearrangement, as well as nitrogen ylide formation followed by azetidine ring expansion. The initial reaction can be paired with a subsequent tandem cascade sequence involving dipole formation/cycloaddition in either an intra- or intermolecular sense to generate poly,cyclic N-heterocycles in one pot, with the formation up to three new rings in a single operation. Excellent diastereoselectivity was observed in the intramolecular cycloaddition reaction producing 5 to 7-membered rings.