PHOTOLYSIS OF DIAZOCARBONYL COMPOUNDS IN ALLYLIC ALCOHOLS - NEW PREPARATION OF BICYCLO[3.1.0]LACTONES AND NATURE OF REACTIVE INTERMEDIATE
PHOTOLYSIS OF DIAZOCARBONYL COMPOUNDS IN ALLYLIC ALCOHOLS - NEW PREPARATION OF BICYCLO[3.1.0]LACTONES AND NATURE OF REACTIVE INTERMEDIATE
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DOI：
10.1021/jo00796a006
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发表时间：
1972-01-01
影响因子：
3.6
通讯作者：
MIGITA, T
中科院分区：
文献类型：
--
作者：
ANDO, W;IMAI, I;MIGITA, T
由重氮丙二酸二甲酯或重氮乙酸乙酯光化学生成的碳烷氧基卡宾与烯丙醇反应形成双环[3.1]。0]内酯和卡宾插入烯丙醇的OH键的产物。Bicy clo [3.1. 0]内酯是通过将卡宾加成到C= C双键上，然后通过内酯化消除甲醇而形成的。在与烯丙基醚的反应中也观察到类似的C= C键加成和烷氧羰基卡宾插入C-0键。在光敏化反应中没有观察到插入C-O键或O·-H键的产物，推测该反应生成三重态卡宾。我们最近报道了烷氧羰基卡宾与脂肪族硫化物1 -3和含硫、氧、卤的烯丙基化合物的反应。4-7对于烯丙基化合物如烯丙基正丁基硫醚，主要过程是碳烷氧基卡宾插入C-S键，以及卡宾加成到C= C键。这些反应大多是通过重氮羰基化合物直接光解生成的单重态卡宾反应生成叶立德进行的，而插入产物则是通过2，3-σ迁移烯丙基化反应生成的
Carboalkoxycarbenes, generated photochemically from dimethyl diazomalonate or ethyl diazoacetate, react with allylic alcohols to formbicy clo [3.1. 0] lactones and the insertion products of the carbene into the OH bonds of allylic alcohols. Bicy clo [3.1. 0] lactone is formed by the addition of the carbene to C= C double bond, followed by lactonization with elimination of methanol. Similar addition to the C= C bond and insertion into C—0 bond by carboalkoxycarbenes were also observed in the reaction with allylic ethers. Theproduct of insertion into C—O bond or 0·—H bond was not observed in the photosensitized reaction which is presumed to produce the triplet carbene. It is concluded that the singletstate of carboalkoxycarbene attacks the oxygen atom of the allylic alcohol or ether to give an intermediate oxygen ylide which rearranges to insertion product by 2, 3-sigma-tropic process or to OH insertion product by hydrogen migration.We recently reported a study of the reaction of carbo-alkoxycarbene with aliphatic sulfides1-3 and allylic compounds containing sulfur, oxygen, and halides. 4-7 With an allylic compound such as allyl n-butyl sulfide the major processes were the insertion of the carbo-alkoxycarbene into the C—S bond, and addition of the carbene to the C= C bond. It was proposed that most of these reactions proceed through ylide formation by reaction of the singlet carbenes formed by the direct photolysis of diazocarbonyl compounds, and the inser-tion products were obtained via 2, 3-sigmatropic allylic