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双环金属化吲唑和苯并咪唑手性铱配合物的合成与不对称催化。

Bis-Cyclometalated Indazole and Benzimidazole Chiral-at-Iridium Complexes: Synthesis and Asymmetric Catalysis.

机构信息

Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.

出版信息

Molecules. 2021 Mar 24;26(7):1822. doi: 10.3390/molecules26071822.

DOI:10.3390/molecules26071822
PMID:33804954
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC8037582/
Abstract

A new class of bis-cyclometalated iridium(III) catalysts containing two inert cyclometalated 6--butyl-2-phenyl-2-indazole bidentate ligands or two inert cyclometalated 5--butyl-1-methyl-2-phenylbenzimidazoles is introduced. The coordination sphere is complemented by two labile acetonitriles, and a hexafluorophosphate ion serves as a counterion for the monocationic complexes. Single enantiomers of the chiral-at-iridium complexes (>99% er) are obtained through a chiral-auxiliary-mediated approach using a monofluorinated salicyloxazoline and are investigated as catalysts in the enantioselective conjugate addition of indole to an α,β-unsaturated 2-acyl imidazole and an asymmetric Nazarov cyclization.

摘要

介绍了一类新型双环金属铱(III)催化剂,它含有两个惰性的环金属化 6--丁基-2-苯基-2-苯并咪唑双齿配体或两个惰性的环金属化 5--丁基-1-甲基-2-苯基苯并咪唑。配位球由两个不稳定的乙腈分子补充,六氟磷酸根离子作为单阳离子配合物的抗衡离子。通过使用单氟化水杨醛恶唑啉的手性辅助介导方法,可以获得手性铱配合物的单一对映异构体(>99%ee),并将其作为催化剂用于吲哚与α,β-不饱和 2-酰基咪唑的对映选择性共轭加成反应和不对称 Nazarov 环化反应中。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/d276545da784/molecules-26-01822-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/3f58b1c3a288/molecules-26-01822-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/7a8164040321/molecules-26-01822-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/603b4a82a59f/molecules-26-01822-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/c284df051f7f/molecules-26-01822-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/d276545da784/molecules-26-01822-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/3f58b1c3a288/molecules-26-01822-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/7a8164040321/molecules-26-01822-sch001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/603b4a82a59f/molecules-26-01822-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/c284df051f7f/molecules-26-01822-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/312a/8037582/d276545da784/molecules-26-01822-g004.jpg

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本文引用的文献

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Acc Chem Res. 2019 Mar 19;52(3):833-847. doi: 10.1021/acs.accounts.9b00028. Epub 2019 Mar 6.
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