Reaction of (1,omega)-N-acylamino alcohols with Lawesson's reagent: Synthesis of sulfur-containing heterocycles
Reaction of (1,omega)-N-acylamino alcohols with Lawesson's reagent: Synthesis of sulfur-containing heterocycles
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DOI：
10.1021/jo961704n
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发表时间：
1997-02-21
影响因子：
3.6
通讯作者：
Nishio, T
中科院分区：
文献类型：
--
作者：
Nishio, T
Lawesson试剂[LR：2，4-双（对-甲氧基苯基）-1，3，2，4-二硫杂磷杂环己烷2，4-二硫化物]被证明是一种有价值的试剂，用于容易地获得含硫杂环：从（1，2）-N-酰氨基醇1开始的噻唑啉2和从[2-（N-酰氨基）苯基]链烷醇1,2开始的苯并噻嗪14。用LR处理（1，2）-N-酰氨基仲醇1a-p，通过将醇直接转化为相应的硫醇，随后将酰胺羰基硫化，然后环化并消除硫化氢，得到噻唑啉1a-p。然而，（1，2）-N-酰氨基叔醇1 q-u与LR反应产生脱水产物5-7和9。用摩尔当量的LR处理[2-（N-酰氨基）苯基]链烷醇12 a-f得到3，1-苯并噻嗪14 a-f。在该反应中，当用0.5当量LR处理相应的醇12 a-e时，分离出[2-（N-酰氨基）苯基]烷硫醇13 a-e。13 c用LR进一步硫化也得到3，1-苯并噻嗪14 c。
Lawesson's reagent [LR: 2,4-bis(p-methoxyphenyl)-1,3,2,4-dithiaphosphetane 2,4-disulfide] is shown to be a valuable reagent for the ready access of sulfur-containing heterocycles: thiazolines 2 starting from the (1,2)-N-acylamino alcohols 1 and benzothiazines 14 from [2-(N-acylamino)phenyl]alkanols 12. Treatment of (1,2)-N-acylamino secondary alcohols 1a-p with LR gave the thiazolines 1a-p via direct conversion of the alcohols to the respective thiols, and the subsequent thionation of the amide carbonyl, followed by cyclization with the elimination of hydrogen sulfide. However, reaction of (1,2)-N-acylamino tertiary alcohols 1q-u with LR yielded the dehydration products 5-7 and 9. Treatment of [2-(N-acylamino)phenyl]alkanols 12a-f with a molar equivalent of LR yielded the 3,1-benzothiazines 14a-f. In this reaction, the [2-(N-acylamino)phenyl]alkanethiols 13a-e were isolated when the corresponding alcohols 12a-e were treated with 0.5 equiv of LR. Further thionation of 13c with LR also gave 3,1-benzothiazine 14c.