Neighboring effect of the lactam functionality in select reactions of 6-azaspiro[4.5]decane-1,7-dione
Neighboring effect of the lactam functionality in select reactions of 6-azaspiro[4.5]decane-1,7-dione
复制标题
DOI：
10.1016/j.tet.2005.08.091
复制
发表时间：
2005-11-14
期刊：
影响因子：
2.1
通讯作者：
Paquette, LA
中科院分区：
文献类型：
--
作者：
Hilmey, DG;Gallucci, JC;Paquette, LA
评估了 6-azaspiro[4.5]decane-1,7-dione (4) 对亲核攻击的敏感性。尽管空间效应阻碍了许多试剂的 1,2-加成，但更具反应性的锂和格氏物质会发生反应。从顺式到内酰胺官能团方向的攻击占主导地位。选定产物的酸催化重排产生烯丙醇，其双键距螺环碳的距离不同。这些设计的系统主要从π表面顺式氢化成酰胺组分，当羟基靠近这些杂原子时更是如此。当 N-苯甲酰化中间体在甲醇中用碳酸钾水解时，会发生相同的现象。 (c) 2005 Elsevier Ltd. 保留所有权利。
The susceptibility of 6-azaspiro[4.5]decane-1,7-dione (4) to nucleophilic attack was evaluated. Although steric effects preclude the 1,2-addition of many reagents, more reactive lithium and Grignard species react. Attack from the direction syn to the lactam functionality predominates. The acid-catalyzed rearrangement of select products delivered allylic alcohols carrying their double bond at varying distances from the spirocyclic carbon. These designed systems undergo hydrogenation predominantly from that pi-surface syn to the amide component, the more so when a hydroxyl is proximate to these hetero atoms. The same phenomenon operates when N-benzoylated intermediates are hydrolyzed with potassium carbonate in methanol. (c) 2005 Elsevier Ltd. All rights reserved.