Favorskii-Type Rearrangement of the 4,5-Epoxymorphinan Skeleton
Favorskii-Type Rearrangement of the 4,5-Epoxymorphinan Skeleton
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4,5-环氧吗啡喃骨架的 Favorskii 型重排
DOI：
10.1021/acs.orglett.8b00288
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发表时间：
2018
期刊：
影响因子：
5.2
通讯作者：
Nagase Hiroshi
中科院分区：
文献类型：
--
作者：
Kutsumura Noriki;Koyama Yasuaki;Suzuki Yuko;Tominaga Ken-ichi;Yamamoto Naoshi;Saitoh Tsuyoshi;Nagumo Yasuyuki;Nagase Hiroshi
纳洛酮与各种芳醛的羟醛缩合反应高产率地得到相应的7-亚苄基纳洛酮衍生物。然而，新的C-环收缩吗啡喃化合物时，2-吡啶甲醛或其相关的类似物被用作偶联伴侣。关键的结构特征是吗啡喃骨架的四氢呋喃环（4，5-环氧环，E-环）的存在。反应体系的时间分辨原位红外光谱表明，扭曲的环丙酮中间体存在短暂的吸收。
The aldol condensation of naltrexone with various aryl aldehydes gives the corresponding 7-benzylidenenaltrexone derivatives in high yields. However, novel C-ring-contracted morphinan compounds were produced when 2-pyridinecarboxaldehyde or its related analogues were used as a coupling partner. The key structural feature was the existence of the tetrahydrofuran ring (4,5-epoxy ring, E-ring) of the morphinan skeleton. The time-resolved in situ IR spectroscopy of the reaction system indicated the short-lived absorption of the distorted cyclopropanone intermediate.