TRANSITION METAL-MEDIATED REACTIONS USING [C-11] CYANIDE IN SYNTHESIS OF C-11 LABELED AROMATIC-COMPOUNDS
TRANSITION METAL-MEDIATED REACTIONS USING [C-11] CYANIDE IN SYNTHESIS OF C-11 LABELED AROMATIC-COMPOUNDS
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DOI：
10.1039/p19940001395
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发表时间：
1994-06-07
期刊：
影响因子：
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通讯作者：
LANGSTROM, B
中科院分区：
文献类型：
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作者：
ANDERSSON, Y;LANGSTROM, B
芳族和杂芳族腈。用氰基中的碳-II标记的，已经通过使用[C-11]氰化氢的快速钯和铬介导的反应合成。芳基碘化物、溴化物和三氟甲磺酸酯的C-11-氰化反应。或在杂芳族溴化物上，在5分钟内，用三苯膦钯催化的C-11氰化反应的放化产率为54-99%，反应中底物浓度变化，反应的范围降低到亚微摩尔级（>0.1 μ mol），经半制备型HPLC纯化后，[氰基-C-11]苯甲腈的衰变校正放射化学产率为50- 90%，以[C-11]氰化氢计，总合成时间为20-25 min，放射化学纯度> 98%。在某些氟代芳烃的三羰基铬络合物上用C-11-氰化物进行亲核芳族取代，放射化学产率为46- 74%。在一个组合的合成序列中，Pd-0辅助的氯代芳烃（三羰基）铬配合物的C-11-氰化，放射化学产率为95%。以1，4-二溴苯为原料，经单-C-11-氰化反应，得到双官能团前体4-溴[氰基-C-11]苯甲腈。随后在四（三苯基膦）钯存在下与苯基（三甲基）锡交叉偶联，以60%的放射化学产率得到4-[氰基-C-11]联苯腈。纯化前的合成时间为从轰击结束算起的15分钟。
Aromatic and heteroaromatic nitriles. labelled with carbon-ii in the cyano group, have been synthesized by rapid palladium- and chromium-mediated reactions using hydrogen [C-11]cyanide. The C-11-cyanation on aryl iodides, bromides, and triflate. or on heteroaromatic bromides, in the presence of tetrakis(triphenylphosphine)palladium, afforded 54-99% radiochemical yield in 5 min. The Pd-0-promoted C-11-cyanation was performed with varying concentrations of substrate, down to the submicro molar scale (>0.1 mu mol), The decay-corrected radiochemical yields of [cyano-C-11]benzonitriles after purification by semi-preparative HPLC were 50-90%, based on hydrogen [C-11]cyanide, with a total synthesis time of 20-25 min and a radiochemical purity > 98%. Nucleophilic aromatic substitution with C-11-cyanide on tricarbonylchromium complexes of some fluoroarenes resulted in radiochemical yields of 46-74%. In a combined synthetic sequence, Pd-0-assisted C-11-cyanation on chloroarene(tricarbonyl)chromium complexes, the radiochemical yields were 95%. By mono-C-11-cyanation on 1,4-dibromobenzene, the difunctional precursor 4-bromo[cyano-C-11]benzonitrile was obtained. Subsequent cross-coupling with phenyl (trimethyl)tin in the presence of tetrakis(triphenylphosphine)palladium afforded 4-[cyano-C-11]biphenylcarbonitrile in 60% radiochemical yield. The synthesis time before purification was 15 min counted from end of bombardment.