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Catalytic Cleavage of Carbon Unreactive Bonds by the Coordination of a Directing Group

通过指导基团的协调催化裂解碳惰性键

基本信息

批准号：
13450364
负责人：
CHATANI Naoto
金额：
$ 10.75万
依托单位：
Osaka University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

(1)Catalytic reactions which involve the cleavage of an sp^3 C-H bond adjacent to a nitrogen atom in N-2-pyridynyl alkylamines are explored. The use of Ru_3(CO)_<12> as the catalyst results in the addition of the sp^3C-H bond across alkene bond to give the coupling products. A variety of alkenes, including terminal, internal, and cyclic alkenes, can be used for the coupling reaction. The presence of directing groups, such as pyridine, pyrimidine, and an oxazoline ring, on the nitrogen of the amine is critical for a successful reaction.(2)The reaction of pyrydinyl esters with HCOONH_4 in the presence of Ru_3(CO)_<12> resulted in decarbonylative reduction to give hydrocarbons. The use of organoboron compounds as a coupling partner resulted in cross-coupling reaction to give ketones, and no decarbonylation took place. A hydrosilane can also be used as a reducing reagent in place of HCOONH_4. A wide variety of functional groups are compatible for both reactions. The key step for both catal … More ytic reactions is the directing group-promoted cleavage of an acyl carbon-oxygen bond in esters, leading to the generation of acyl transition metal alkoxo complexes.(3)The direct carbonylation of C-H bonds in the benzene ring of N-phenylpyrazoles via catalysis by ruthenium or rhodium complexes was achieved. The reaction of N-phenylpyrazoles with carbon monoxide and ethylene in the presence of Ru_3(CO)_<12> or Rh_4(CO)_<12> resulted in the siteselective carbonylation of the ortho C-H bonds in the benzene ring to give the corresponding ethylketones. A variety of functional groups on the benzene ring can be tolerated. N-Phenylpyrazoles have higher reactivities than would be expected, based on the pKa values of the conjugate acid of pyrazole. The choice of solvent for this reaction is significant, and N, N-dimethylacetamide (DMA) gives the best result.(4)The reaction of alkenes with pyridinemethanol and CO in the presence of Rh_4(CO)_<12> resulted in hydroesterification under relatively mild reaction conditions. The use of benzyl alcohol in place of pyridinemethanol gave no reaction. Less

（1）探索了N-2-吡啶基烷基胺中与氮原子相邻的sp^3 C-H键断裂的催化反应。以Ru_3（CO）_<12>为催化剂，在烯烃键上加成sp^3C-H键，得到偶联产物。各种烯烃，包括末端烯烃、内部烯烃和环状烯烃，可用于偶联反应。在胺的氮上存在导向基团，如吡啶、嘧啶和恶唑啉环，对于成功的反应是至关重要的。（2）吡啶基酯在Ru_3（CO）_4存在下与HCOONH_4反应，<12>脱羰基还原生成烃类化合物。使用有机硼化合物作为偶联伙伴导致交叉偶联反应生成酮，并且没有发生脱羰基反应。氢化硅烷也可代替HCOONH_4用作还原剂。各种各样的官能团对于两种反应都是相容的。两种催化剂的关键步骤 ...更多信息裂解反应是酯中酰基碳-氧键的定向基团促进的裂解，导致酰基过渡金属烷氧基络合物的产生。（3）在钌或铑配合物催化下，N-苯基吡唑类化合物苯环上的C-H键直接羰基化。在Ru_3（CO）_或Rh_4（CO）_存在下，N-苯基吡唑与CO和乙烯反应<12>，<12>苯环上的邻位C-H键发生位置选择性羰基化反应，生成相应的乙基酮。苯环上的各种官能团都是可以接受的。N-苯基吡唑具有比基于吡唑的共轭酸的pKa值预期的更高的反应性。溶剂的选择对该反应有重要意义，N，N-二甲基乙酰胺（DMA）的效果最好。（4）在Rh_4（CO）_3存在下，烯烃与吡啶甲醇和CO的反应<12>在相对温和的条件下发生氢酯基化反应。用苯甲醇代替吡啶甲醇，没有反应。少