Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state
Solid-state [2+2] photochemical cycloaddition reactions have been extensively studied after the classical work of Schmidt in the 1960s. Of these, trans-1,2-bis(4′-pyridyl)ethylene (bpe) is one of the well-studied alkenes to synthesize tetrakis(4-pyridyl)cyclobutane (tpcb). However, almost all the so...
| Những tác giả chính: | , , , , , , |
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| Định dạng: | Journal Article |
| Ngôn ngữ: | English |
| Được phát hành: |
2015
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| Những chủ đề: | |
| Truy cập trực tuyến: | https://hdl.handle.net/10356/107432 http://hdl.handle.net/10220/25623 http://dx.doi.org/10.1002/chem.201405228 |
| _version_ | 1826125849272778752 |
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| author | Chanthapally, Anjana Yang, Hui Quah, Hong Sheng Webster, Richard D. Schreyer, Martin K. Wong, Ming Wah Vittal, Jagadese J. |
| author2 | School of Physical and Mathematical Sciences |
| author_facet | School of Physical and Mathematical Sciences Chanthapally, Anjana Yang, Hui Quah, Hong Sheng Webster, Richard D. Schreyer, Martin K. Wong, Ming Wah Vittal, Jagadese J. |
| author_sort | Chanthapally, Anjana |
| collection | NTU |
| description | Solid-state [2+2] photochemical cycloaddition reactions have been extensively studied after the classical work of Schmidt in the 1960s. Of these, trans-1,2-bis(4′-pyridyl)ethylene (bpe) is one of the well-studied alkenes to synthesize tetrakis(4-pyridyl)cyclobutane (tpcb). However, almost all the solid-state [2+2] cycloaddition reactions of bpe yielded, almost exclusively, one of the four possible isomers, namely, the rctt-tpcb (r=regio c=cis and t=trans). Here we describe a stereoselective synthesis of the tetrahedrally disposed rtct-tpcb by the solid-state thermal isomerization of the rctt-isomer in atmospheric air. We propose that this isomerization occurs through a topochemical unimolecular mechanism by a radical chain pathway, initiated by molecular oxygen. This is supported by the nature of products formed in air and nitrogen, detection of a radical in ESR spectral studies, ESI-MS crossover experiments, VT PXRD studies along with QM, MD and docking calculations. The formation of a unique isomer by thermal isomerization may be a general phenomenon to quantitatively synthesize other useful stereoisomers from the existing isomers of cyclobutane derivatives. |
| first_indexed | 2024-10-01T06:43:25Z |
| format | Journal Article |
| id | ntu-10356/107432 |
| institution | Nanyang Technological University |
| language | English |
| last_indexed | 2024-10-01T06:43:25Z |
| publishDate | 2015 |
| record_format | dspace |
| spelling | ntu-10356/1074322019-12-06T22:30:59Z Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state Chanthapally, Anjana Yang, Hui Quah, Hong Sheng Webster, Richard D. Schreyer, Martin K. Wong, Ming Wah Vittal, Jagadese J. School of Physical and Mathematical Sciences DRNTU::Science::Chemistry::Organic chemistry::Oxidation Solid-state [2+2] photochemical cycloaddition reactions have been extensively studied after the classical work of Schmidt in the 1960s. Of these, trans-1,2-bis(4′-pyridyl)ethylene (bpe) is one of the well-studied alkenes to synthesize tetrakis(4-pyridyl)cyclobutane (tpcb). However, almost all the solid-state [2+2] cycloaddition reactions of bpe yielded, almost exclusively, one of the four possible isomers, namely, the rctt-tpcb (r=regio c=cis and t=trans). Here we describe a stereoselective synthesis of the tetrahedrally disposed rtct-tpcb by the solid-state thermal isomerization of the rctt-isomer in atmospheric air. We propose that this isomerization occurs through a topochemical unimolecular mechanism by a radical chain pathway, initiated by molecular oxygen. This is supported by the nature of products formed in air and nitrogen, detection of a radical in ESR spectral studies, ESI-MS crossover experiments, VT PXRD studies along with QM, MD and docking calculations. The formation of a unique isomer by thermal isomerization may be a general phenomenon to quantitatively synthesize other useful stereoisomers from the existing isomers of cyclobutane derivatives. 2015-05-20T04:05:07Z 2019-12-06T22:30:59Z 2015-05-20T04:05:07Z 2019-12-06T22:30:59Z 2014 2014 Journal Article Chanthapally, A., Yang, H., Quah, H. S., Webster, R. D., Schreyer, M. K., Wong, M. W., et al. (2014). Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state. Chemistry - a European journal, 20(48), 15702-15708. 0947-6539 https://hdl.handle.net/10356/107432 http://hdl.handle.net/10220/25623 http://dx.doi.org/10.1002/chem.201405228 en Chemistry - a European journal © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
| spellingShingle | DRNTU::Science::Chemistry::Organic chemistry::Oxidation Chanthapally, Anjana Yang, Hui Quah, Hong Sheng Webster, Richard D. Schreyer, Martin K. Wong, Ming Wah Vittal, Jagadese J. Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| title | Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| title_full | Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| title_fullStr | Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| title_full_unstemmed | Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| title_short | Oxygen-initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| title_sort | oxygen initiated stereoselective thermal isomerisation of a cyclobutane derivative in the solid state |
| topic | DRNTU::Science::Chemistry::Organic chemistry::Oxidation |
| url | https://hdl.handle.net/10356/107432 http://hdl.handle.net/10220/25623 http://dx.doi.org/10.1002/chem.201405228 |
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