ORTHO-FUNCTIONALIZATION OF AROMATIC KETONES VIA MANGANATION - A SYNTHESIS OF INDENOLS
ORTHO-FUNCTIONALIZATION OF AROMATIC KETONES VIA MANGANATION - A SYNTHESIS OF INDENOLS
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DOI：
10.1021/jo00264a030
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发表时间：
1989-02-03
影响因子：
3.6
通讯作者：
TREMONT, SJ
中科院分区：
文献类型：
--
作者：
LIEBESKIND, LS;GASDASKA, JR;TREMONT, SJ
结果经改良Kaesz法，48（t？）以苯乙酮为原料，在正庚烷中与PhCH_2 Mn（CO）_（57）反应，高产率地合成了2-（2-乙酰基苯基）四羰基锰（1）。在各种炔存在下，1的热分解或光解未能诱导清洁反应。然而，1的黄色溶液的脱羰基活化是通过在乙腈中用无水三甲基胺N-氧化物8（TMANO）短暂处理来完成的。9在向所得的红橙色溶液中加入炔时，在8-16小时的过程中发生缓慢反应，同时颜色变为浅黄橙色，导致以良好的产率产生茚醇2（表I）。从表I中的结果可以看出，茚-烯醇合成是非常普遍的，用末端、内部、富电子和缺电子的炔进行，并且该反应表现出令人惊讶的区域化学程度
ResultsVia a modification of the procedure of Kaesz, 48 (t? 2-2-acetylphenyl) tetracarbonylmanganese (1) was prepared in high yield by heating acetophenone with PhCH2Mn (CO) 57 in heptane. Thermolysis or photolysis of 1 in the presence of a variety of alkynes failed to induce a clean reaction. However, decarbonylative activation of a yellow solution of 1 was accomplished by brief treatment with anhydrous trimethylamine N-oxide8 (TMANO) in acetonitrile. 9 On addition of alkyne to the resulting reddish-orange solution, a slow reaction occurred over the course of 8-16 h con-current with a color change to pale yellow-orange resulting in production of the indenols 2 in good yields (Table I). It can be seen from the results in Table I that the in-denol synthesis is very general, proceeding with terminal, internal, electron-rich, and electron-deficient alkynes, and the reaction exhibited a surprising degree of regiochemical