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适用于催化的手性CpRh和Ir配合物的温和络合方案。

Mild complexation protocol for chiral CpRh and Ir complexes suitable for catalysis.

作者信息

Audic B, Wodrich M D, Cramer N

机构信息

Laboratory of Asymmetric Catalysis and Synthesis , EPFL SB ISIC LCSA, BCH 4305 , CH-1015 Lausanne , Switzerland . Email:

Laboratory for Computational Molecular Design , EPFL SB ISIC LCMD, BCH 5312 , CH-1015 Lausanne , Switzerland . Email:

出版信息

Chem Sci. 2018 Oct 31;10(3):781-787. doi: 10.1039/c8sc04385j. eCollection 2019 Jan 21.

DOI:10.1039/c8sc04385j
PMID:30774871
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6346397/
Abstract

A practical complexation method for chiral cyclopentadienyl (Cp) iridium and rhodium complexes is described. The procedure uses the free CpH with stable and commercially available rhodium(i) and iridium(i) salts without base or additive. The conditions are mild and do not require the exclusion of air and moisture. A salient feature is the suitability for complexations enhancing the user-friendliness of Cp ligands in asymmetric catalysis. DFT-calculations confirm an intramolecular proton abstraction pathway by either the bound acetate or methoxide. Furthermore, the superior facial selectivity of the proton abstraction step enabled the development of TMS-containing trisubstituted Cp ligands which display improved enantioselectivities for the benchmarking dihydroisoquinolone synthesis.

摘要

描述了一种用于手性环戊二烯基（Cp）铱和铑配合物的实用络合方法。该方法使用游离的CpH与稳定且市售的铑（I）和铱（I）盐，无需碱或添加剂。条件温和，不需要排除空气和水分。一个显著特点是适合络合，提高了Cp配体在不对称催化中的用户友好性。密度泛函理论（DFT）计算证实了通过结合的乙酸根或甲醇根的分子内质子提取途径。此外，质子提取步骤的卓越面选择性使得能够开发含TMS的三取代Cp配体，这些配体在基准二氢异喹啉酮合成中显示出改进的对映选择性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/83e5225275f2/c8sc04385j-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/28130c83eddf/c8sc04385j-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/0075aad07838/c8sc04385j-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/3c97d9da5675/c8sc04385j-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/8c74bec13701/c8sc04385j-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/cd1d961f15cb/c8sc04385j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/f50c39badec3/c8sc04385j-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/83e5225275f2/c8sc04385j-s6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/28130c83eddf/c8sc04385j-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/97c7d63b6bc6/c8sc04385j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/0075aad07838/c8sc04385j-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/3c97d9da5675/c8sc04385j-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/8c74bec13701/c8sc04385j-s4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/cd1d961f15cb/c8sc04385j-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/f50c39badec3/c8sc04385j-s5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/11aa/6346397/83e5225275f2/c8sc04385j-s6.jpg

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