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通过无氢受体铱催化的脱氢C-H硅基化实现三氟甲基化叔苯甲醇的对映选择性去对称化：三氟甲基的决定性作用

Enantioselective Desymmetrization of Trifluoromethylated Tertiary Benzhydrols via Hydrogen-Acceptor-Free Ir-Catalyzed Dehydrogenative C-H Silylation: Decisive Role of the Trifluoromethyl Group.

作者信息

Yamamoto Yoshihiko, Tadano Ryu, Yasui Takeshi

机构信息

Department of Basic Medicinal Sciences, Graduate School of Pharmaceutical Sciences, Nagoya University, Chikusa, Nagoya 464-8601, Japan.

出版信息

JACS Au. 2024 Feb 15;4(2):807-815. doi: 10.1021/jacsau.3c00794. eCollection 2024 Feb 26.

DOI:10.1021/jacsau.3c00794
PMID:38425931
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10900501/
Abstract

Although the trifluoromethyl (CF) group is one of the most important fluorinated groups owing to its significant ability to modulate pharmacological properties, constructing trifluoromethylated stereogenic centers in an enantioselective manner has been a formidable challenge. Herein, we report the development of the enantioselective desymmetrization of trifluoromethylated benzhydrols via intramolecular dehydrogenative silylation using Ir catalysts with chiral pyridine-oxazoline (PyOX) ligands. The produced benzoxasilol was transformed into several unsymmetrical benzhydrols via iododesilylation and subsequent transition-metal-catalyzed cross-coupling reactions. Moreover, the same Ir catalyst system was used for the kinetic resolution of unsymmetrical trifluoromethylated benzhydrols.

摘要

尽管三氟甲基（CF）基团因其显著调节药理性质的能力而成为最重要的氟化基团之一，但以对映选择性方式构建三氟甲基化的手性中心一直是一项艰巨的挑战。在此，我们报道了使用具有手性吡啶-恶唑啉（PyOX）配体的铱催化剂，通过分子内脱氢硅烷化实现三氟甲基化二苯甲醇的对映选择性去对称化反应。生成的苯并硅氧烷通过碘代脱硅烷化及随后的过渡金属催化交叉偶联反应转化为几种不对称二苯甲醇。此外，相同的铱催化剂体系用于不对称三氟甲基化二苯甲醇的动力学拆分。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/d6c1a63dc865/au3c00794_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/14f016d99f1c/au3c00794_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/abe0de60f11d/au3c00794_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/537f54336385/au3c00794_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/3e77bfa154fc/au3c00794_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/d79a625944a9/au3c00794_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/e2785ef205b0/au3c00794_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/d6c1a63dc865/au3c00794_0007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/14f016d99f1c/au3c00794_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/abe0de60f11d/au3c00794_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/537f54336385/au3c00794_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/3e77bfa154fc/au3c00794_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/d79a625944a9/au3c00794_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/e2785ef205b0/au3c00794_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a6cb/10900501/d6c1a63dc865/au3c00794_0007.jpg

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本文引用的文献

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