Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers
The synthesis of a new CF<sub>3</sub>-containing stereogenic atropisomeric pair of ortho-disubstituted biphenyl scaffold is presented. The atropisomers are surprisingly conformationally stable for isolation. X-ray structures show that their stability comes from an intramolecular hydrogen...
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MDPI AG
2019-02-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/24/3/643 |
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doaj-6b06fed66d4c40739987fe686e5cfd812020-11-25T02:46:23ZengMDPI AGMolecules1420-30492019-02-0124364310.3390/molecules24030643molecules24030643Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic CentersChi-Tung Yeung0Wesley Ting Kwok Chan1Wai-Sum Lo2Ga-Lai Law3Wing-Tak Wong4The Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen 518000, PR ChinaState Key Laboratory of Chemical Biology and Drug Discovery, Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon 999077, Hong KongThe Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen 518000, PR ChinaThe Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen 518000, PR ChinaThe Hong Kong Polytechnic University Shenzhen Research Institute, Shenzhen 518000, PR ChinaThe synthesis of a new CF<sub>3</sub>-containing stereogenic atropisomeric pair of ortho-disubstituted biphenyl scaffold is presented. The atropisomers are surprisingly conformationally stable for isolation. X-ray structures show that their stability comes from an intramolecular hydrogen bond formation from their two hydroxyl groups and renders the spatial arrangement of their peripheral CF<sub>3</sub> and CH<sub>3</sub> groups very different. The synthesized stereogenic scaffold proved to be effective in catalyzing the asymmetric <i>N</i>-nitroso aldol reaction of enamine and nitrosobenzene. Compared to similar scaffolds without CF<sub>3</sub> groups, one of our atropisomer exhibits an increase in enantioselectivity in this reaction.https://www.mdpi.com/1420-3049/24/3/643atropisomerasymmetryhydrogen bond<i>N</i>-nitroso aldol reaction |
| collection |
DOAJ |
| language |
English |
| format |
Article |
| sources |
DOAJ |
| author |
Chi-Tung Yeung Wesley Ting Kwok Chan Wai-Sum Lo Ga-Lai Law Wing-Tak Wong |
| spellingShingle |
Chi-Tung Yeung Wesley Ting Kwok Chan Wai-Sum Lo Ga-Lai Law Wing-Tak Wong Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers Molecules atropisomer asymmetry hydrogen bond <i>N</i>-nitroso aldol reaction |
| author_facet |
Chi-Tung Yeung Wesley Ting Kwok Chan Wai-Sum Lo Ga-Lai Law Wing-Tak Wong |
| author_sort |
Chi-Tung Yeung |
| title |
Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers |
| title_short |
Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers |
| title_full |
Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers |
| title_fullStr |
Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers |
| title_full_unstemmed |
Synthesis of a Conformationally Stable Atropisomeric Pair of Biphenyl Scaffold Containing Additional Stereogenic Centers |
| title_sort |
synthesis of a conformationally stable atropisomeric pair of biphenyl scaffold containing additional stereogenic centers |
| publisher |
MDPI AG |
| series |
Molecules |
| issn |
1420-3049 |
| publishDate |
2019-02-01 |
| description |
The synthesis of a new CF<sub>3</sub>-containing stereogenic atropisomeric pair of ortho-disubstituted biphenyl scaffold is presented. The atropisomers are surprisingly conformationally stable for isolation. X-ray structures show that their stability comes from an intramolecular hydrogen bond formation from their two hydroxyl groups and renders the spatial arrangement of their peripheral CF<sub>3</sub> and CH<sub>3</sub> groups very different. The synthesized stereogenic scaffold proved to be effective in catalyzing the asymmetric <i>N</i>-nitroso aldol reaction of enamine and nitrosobenzene. Compared to similar scaffolds without CF<sub>3</sub> groups, one of our atropisomer exhibits an increase in enantioselectivity in this reaction. |
| topic |
atropisomer asymmetry hydrogen bond <i>N</i>-nitroso aldol reaction |
| url |
https://www.mdpi.com/1420-3049/24/3/643 |
| work_keys_str_mv |
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