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基于三氟甲基砌块的催化不对称傅-克反应研究进展
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:O623.662[理学—有机化学;理学—化学]
  • 作者机构:[1]四川职业技术学院建筑与环境工程系,遂宁629000, [2]武汉理工大学理学院化学系,武汉430070, [3]武汉理工大学复合材料国家重点实验室,武汉430070
  • 相关基金:四川省教育厅科研项目基金(13ZA0034); 中央高校基本科研业务费专项资金(项目编号:2013-IV-077); 湖北省“楚天学者计划”; 中组部“外专千人计划”资助~~
中文摘要:

引入三氟甲基基团可以显著提高有机分子的化学和代谢稳定性、亲脂性以及在细胞膜中的渗透性,因此发展高效合成三氟甲基化合物,特别是手性三氟甲基化合物的方法具有非常重要的意义.基于三氟甲基砌块的催化不对称傅-克反应可以高效高选择性获得手性三氟甲基芳香化合物,是最近发展起来的一个研究热点.自从日本Mikami小组采用手性钛络合物研究了首例基于三氟甲基砌块的催化不对称傅-克反应,不同种类的手性有机金属催化剂(如手性钛,铜,锌,锆,钯,镱,钇,镍,钙等金属络合物)和手性有机小分子催化剂(如金鸡纳碱,手性脯氨醇硅醚,手性磷酸等)都在这类不对称催化反应中得到应用.作者主要对反应组分(特别是不同类型的三氟甲基砌块)、反应条件、反应机理和合成应用等方面的研究进行了综述.最后,对这类反应所存在的问题和局限性进行了总结,并对今后发展方向作了展望.

英文摘要:

The incorporation of a trifluoromethyl (CF3) group can increase chemical and metabolic stability, lipophilicity, and membrane permeability of the molecules. As a consequence, the exploitation of efficient methods to construct chiral trifluoromethylated compounds is a highly significant task. Two strategies are often utilized to synthesize compounds bearing a CF3 group at the chiral center. The first strategy is the transfer of a CF3 group from a reagent. This strategy seems to be straightforward and practical, but direct enantioselective trifluoromethylation remains a challenge, and high enantioselectivi- ties are rarely reached. An alternative strategy is the application of some established asymmetric catalytic reactions by using trifluoromethylated compounds as building blocks, which could provide various chiral trifluoromethylated products in high yields and enantioselectivities under mild conditions. Asymmetric Friedel-Crafts reaction has witnessed rapid development in recent years. Asymmetric Friedel-Crafts reaction using prochiral trifluoromethylated starting materials represents an impor- tant method for the access of trifluoromethylated derivatives of chiral aromatic compounds. Since Mikami's group identified that chiral BINOL-derived Ti(IV) complexs could be applied in the asymmetric Friedel-Crafts reaction with fluoral to obtain chiral trifluoromethylated compounds, considerable efforts have been dedicated to utilize other chiral organometallic cata- lysts (such as chiral Ti, Cu, Zn, Zr, Pd, Y, Yb, Ni, Ca complex, etc.) and chiral organo-catalysts (such as cinchona alkaloids, chiral prolinol ethers, chiral phosphoric acids, etc.) in this type of catalytic reaction. Chiral trifluoromethylated compounds with a CF3-group at a chiral carbon center with, or without any heteroatom substituents were obtained in high yields and en- antioselectivities. The components (especially CF3-containing starting material of trifluoromethyl ketones, imines and ole- fins), conditions and mechanism of t

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期刊信息
  • 《化学学报》
  • 北大核心期刊(2014版)
  • 主管单位:中国科学院
  • 主办单位:中国化学会 中国科学院上海有机化学研究所
  • 主编:周其林
  • 地址:上海市零陵路345号
  • 邮编:200032
  • 邮箱:hxxb@sioc.ac.cn
  • 电话:021-54925085
  • 国际标准刊号:ISSN:0567-7351
  • 国内统一刊号:ISSN:31-1320/O6
  • 邮发代号:4-209
  • 获奖情况:
  • 首届国家期刊奖,第二届国家期刊奖提名奖,中国期刊方阵“双高期刊”
  • 国内外数据库收录:
  • 俄罗斯文摘杂志,美国化学文摘(网络版),荷兰文摘与引文数据库,美国科学引文索引(扩展库),日本日本科学技术振兴机构数据库,中国中国科技核心期刊,中国北大核心期刊(2004版),中国北大核心期刊(2008版),中国北大核心期刊(2011版),中国北大核心期刊(2014版),英国英国皇家化学学会文摘,中国北大核心期刊(2000版)
  • 被引量:28694