THE EFFECT OF ADDED SILVER-NITRATE ON THE PALLADIUM-CATALYZED ARYLATION OF ALLYLTRIMETHYLSILANES
THE EFFECT OF ADDED SILVER-NITRATE ON THE PALLADIUM-CATALYZED ARYLATION OF ALLYLTRIMETHYLSILANES
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DOI：
10.1021/jo00220a042
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发表时间：
1985-01-01
影响因子：
3.6
通讯作者：
HALLBERG, A
中科院分区：
文献类型：
--
作者：
KARABELAS, K;WESTERLUND, C;HALLBERG, A
结果制备结果见方案I。以烯丙基三甲基硅烷和二苯为原料，采用反式Heck反应条件，得到（E）-1-苯基-3-（三甲基硅烷基）-1-丙烯（1），产率32%。然而，在50 ℃、Me 2SO中、在银离子存在下进行反应，可以以55%的产率分离出异构体（E）-3-苯基-1-（三甲基硅烷基）-1-丙烯（2）。在硝酸银存在下，在120 ℃下使（E）-1，3-双（三甲基硅烷基）-1-丙烯和碘苯经受传统的Heck条件，以53%的产率得到2-苯基-3-（三甲基硅烷基）-1-丙烯（3）。在没有硝酸银的情况下，在120 ℃下得到相同的产物，尽管转化速率较慢。该反应涉及碳-硅键的断裂，因此与乙烯基硅烷的钯催化芳基化有关。5在50 ℃下，在硝酸银存在下，该脱甲硅烷基化反应被完全抑制，从而导致以52%产率形成（Z）-1，3-双-（三甲基甲硅烷基）-2-苯基-1-丙烯（4）。
Results The preparative results of these investigations are sum-marized in Scheme I. Thus (E)-1-phenyl-3-(trimethy 1-silyl)-l-propene (1) was obtained in 32% yield starting from allyltrimethylsilane andiodobenzene by using tra-ditional Heck conditions. However, conducting the reac-tion at 50 C in Me2SO in the presence of silver ions allowed the isolation of theisomer (£)-3-phenyl-1-(trimethylsilyl)-1-propene (2) in 55% yield. Subjecting (£)-l, 3-bis (trimethylsilyl)-l-propene and iodobenzene to traditional Heck conditions in the presence of silver nitrate at 120 C gave 2-phenyl-3-(trimethylsilyl)-l-propene (3) in 53% yield. In the absence of silver nitrate at 120 C the same product is obtained, although the rate of con-version is slower. This reactioninvolves cleavage of a carbon-silicon bond and is thus related to the palladium-catalyzed arylation of vinylsilanes. 5 In the presence of silver nitrate at 50 C, this desilylation was completely suppressed, thusresulting in formation of (Z)-l, 3-bis-(trimethylsilyl)-2-phenyl-1-propene (4) in 52% yield.