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金属催化的不对称氢化反应研究进展与展望
  • ISSN号:0567-7351
  • 期刊名称:《化学学报》
  • 时间:0
  • 分类:O621.34[理学—有机化学;理学—化学]
  • 作者机构:[1]南开大学元素有机化学研究所,天津300071
  • 相关基金:项目受国家自然科学基金、国家重点基础研究发展计划(973计划)(No.2012cB821600)和教育部“111”引智计划(No.B06005)资助.
中文摘要:

手性过渡金属络合物催化的不对称氢化反应是合成光学活性化合物的重要方法.本文从手性配体及手性催化剂、不对称催化新反应、新方法和新策略三个方面简要评述新世纪以来过渡金属催化的不对称氢化反应研究领域的新进展.从新世纪初至今,手性单磷配体得到了复兴,出现了如MonoPhos、SiPhos、DpenPhos等高效单齿亚磷酰胺酯配体;磷原子手性(P-手性)配体也得到了快速发展,如BenzP*、ZhanPhos、TriFer等已成为新的高效手性双膦配体;螺环骨架手性配体成为新世纪手性配体设计合成的亮点,除了SiPhos、SIPHOX、SpinPHOX等高效手性螺环配体外,手性螺环吡啶胺基磷配体SpiroPAP的铱催化剂成为目前最高效的分子催化剂.不对称催化氢化新反应研究也取得了突破,如非保护烯胺、杂芳环化合物及N-H亚胺的氢化等反应都实现了高对映选择性.自组装手性催化剂、树枝状手性催化剂、铁磁性纳米负载的可回收手性催化剂,以及"混合"配体手性催化剂等新方法和新策略也在不对称催化氢化反应中得到了应用.然而,手性过渡金属络合物催化的不对称氢化研究仍然充满挑战,也期待新的突破.

英文摘要:

Chiral transition metal complexes-catalyzed asymmetric hydrogenation is one of the most efficient methods for the synthesis of optically active compounds, and has been intensively investigated in the past decades. This review presents a brief overview on the progress in the transition metal-catalyzed asymmetric hydrogenation since the beginning of this new century from three aspects: (1) chiral ligands and catalysts; (2) new catalytic asymmetric hydrogenations; (3) new methods and new strategies in asymmetric hydrogenations. Chiral monodentate phosphorus ligands have been a renaissance from the beginning of new century, and many efficient chiral monophosphoramidites such as MonoPhos, SiPhos, DpenPhos have been developed. The chiral phosphine ligands with a chirality on the phosphorus atom (P-chirality), such as BenzP, ZhanPhos, and TriFer, have also been explored. Chiral ligands with a spiro skeleton have been a highlight of design and synthesis of chiral ligands. The chiral spiro ligands such as SDP, SiPhos, SIPHOX, and SpinPHOX are very efficient in asymmetric hy- drogenations. The iridium complexes of chiral spiro pyridine-aminophosphine ligands SpiroPAP is the most efficient mo- lecular catalysts up to now with a turnover number (ratio of converted substrate to catalyst) over 4500000 in the hydrogena- tion of acetophenone. A number of breakthroughs have been made in the researches on new catalytic asymmetric hydrogena- tions. Highly enantioslective hydrogenations of unprotected enamines, heteroaromatic compounds, and N-H imines have been developed. New methods and strategies including self-assembled, dendrimerized, and ferromagnetic nanomateri- als-loaded chiral catalysts with recyclability and reusability, the catalysts with "mixed" chiral ligands have also been suc- cessfully applied in the catalytic asymmetric hydrogenations. However, the chiral transition metal complexes catalyzed asymmetric hydrogenation still has many challenges and is looking forward to new breakthroughs in th

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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