Cobalt-Catalyzed Addition Reaction of Organoboronic Acids with Aldehydes: Highly Enantioselective Synthesis of Diarylmethanols
Cobalt-Catalyzed Addition Reaction of Organoboronic Acids with Aldehydes: Highly Enantioselective Synthesis of Diarylmethanols
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DOI：
10.1002/chem.201001160
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发表时间：
2010-01-01
影响因子：
4.3
通讯作者：
Cheng, Chien-Hong
中科院分区：
文献类型：
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作者：
Karthikeyan, Jaganathan;Jeganmohan, Masilamani;Cheng, Chien-Hong
过渡金属催化的有机金属试剂与醛的加成反应是合成取代仲醇的关键方法。[1]各种有机金属试剂，如有机镁、[2]-锌、[1，12E-I]-锂、[3]-硅烷、[4]-锡烷[5]和-硼[6]都被用于这些加成反应。其中，有机硼试剂因其具有对空气和湿度稳定、低毒、易得等优点而备受关注。Rh、[1c，7]Pd、[8]铂、[9a]和[9b，c]镍配合物能有效地催化有机硼酸与醛的加成反应。最近，铜和铁催化的有机硼酸与醛的加成反应也有报道。[10]然而，醛在这两种加成反应中的范围相当有限。只有带有吸电子取代基的芳香醛才能起到很好的作用。[10]尽管文献中有各种金属催化的有机硼酸与醛的加成反应，但只有几篇关于不对称反应的报道。[3a，b，11]，2006年，周等人。报道了Rh催化的芳香族硼酸与芳香醛的对映体选择性加成反应。在该反应中，观察到手性联芳基甲烷醇的对映体过量(Ee)为62-87%。最近，Miyaura和他的同事报道了Ru催化的芳香族硼酸与芳香醛的不对称加成反应。在反应中，观察到预期的手性联芳基甲醇具有良好的对映体过量。[11B]然而，在这些反应中，使用了专门设计的手性配体和昂贵的Ru或Rh催化剂。手性仲醇是芳香族化合物中的关键结构单元。
Transition-metal-catalyzed addition of organometallic reagents to aldehydes is a key method for the synthesis of substituted secondary alcohols.[1] Various organometallic reagents, such as organomagnesium,[2]-zinc,[1, 12e–i]-lithium,[3]-silane,[4]-stannane [5] and-boron,[6] have been used in these addition reactions. Among them, organoboron reagents have gained much attention due to the advantages of air and moisture stability, low toxicity, and availability. Rhodium,[1c, 7] palladium,[8] platinum,[9a] and nickel [9b, c] complexes efficiently catalyzed the addition reaction of organoboronic acids to aldehydes. Recently, copper-and iron-catalyzed addition reaction of organoboronic acid with aldehydes were also reported.[10] However, the scope of aldehydes in these two addition reactions is rather limited. Only aromatic aldehydes with an electron-withdrawing substituent worked well.[10]Despite the fact that various metal-catalyzed addition reactions of organoboronic acids with aldehydes are available in the literature,[6–10] only a few reports on asymmetric reactions were discussed.[3a, b, 11] In 2006, Zhou et al. reported a rhodium-catalyzed enantioselective addition reaction of aromatic boronic acids with aromatic aldehydes.[11a] In the reaction, enantiomeric excess (ee) values of 62–87% for chiral biaryl methanols were observed. Recently, Miyaura and coworkers reported a ruthenium-catalyzed enantioselective addition reaction of aromatic boronic acids with aromatic aldehydes. In the reaction, the expected chiral biarylmethanols were observed in excellent enantiomeric excess.[11b] However, in these reactions specially designed chiral ligands and expensive ruthenium or rhodium catalysts were used. Chiral secondary alcohols are key structural units present in vari-