Efficient radical addition of tertiary amines to alkenes using photochemical electron transfer
Efficient radical addition of tertiary amines to alkenes using photochemical electron transfer
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DOI：
10.1351/pac200678122227
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发表时间：
2006-12-01
影响因子：
1.8
通讯作者：
Pesch, Jens
中科院分区：
文献类型：
--
作者：
Hoffmann, Norbert;Bertrand, Samuel;Pesch, Jens
开发了叔胺（主要是环状衍生物）与缺电子烯烃的有效光诱导自由基加成。该反应应用于吡咯里西啶类生物碱金链花碱和异紫草醇的不对称合成。然后对该方法进行了优化，以添加更多种类的叔胺，特别是无环叔胺。还研究了与不饱和叔胺的自由基串联加成环化反应。使用同位素标记进行的详细机理研究能够优化与 N,N-二烷基苯胺衍生物的相应反应。阐明了用薄荷氧基呋喃酮实现高反应立体选择性的起源。叔胺的自由基加成也可以使用无机半导体作为敏化剂通过非均相光催化进行。
An efficient photoinduced radical addition of tertiary amine, mainly cyclic derivatives, to electron-deficient alkenes was developed. The reaction was applied to the asymmetric synthesis of the pyrrolizidine alkaloids laburnine and isoretronecanol. The method was then optimized for the addition of a larger variety of tertiary amines, in particular acyclic ones. Radical tandem addition cyclization reactions with unsaturated tertiary amines have also been investigated. A detailed mechanistic study using isotopic labeling enabled the optimization of a corresponding reaction with N,N-dialkylaniline derivatives. The origin of the high reaction stereo selectivity achieved with menthyloxyfuranone was elucidated. The radical addition of tertiary amines was also performed with heterogeneous photocatalysis using inorganic semiconductors as sensitizers.