Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes
The reaction of excess TMSCl and LiCCl2Br at low temperature is a technically simple high yield route to TMSCCl2Br. The latter is a stable source of the dichlorobromomethide carbanion, which undergoes 1,4-addition with cyclic nitroalkenes and (E)-fumarates leading to dichlorocyclopropanes after brom...
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| Format: | Article |
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Wiley-VCH Verlag
2016
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| Online Access: | https://eprints.nottingham.ac.uk/32995/ |
| _version_ | 1848794535948189696 |
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| author | Lee, Darren S. Durán-Peña, Maria Jesus Burroughs, Laurence Woodward, Simon |
| author_facet | Lee, Darren S. Durán-Peña, Maria Jesus Burroughs, Laurence Woodward, Simon |
| author_sort | Lee, Darren S. |
| building | Nottingham Research Data Repository |
| collection | Online Access |
| description | The reaction of excess TMSCl and LiCCl2Br at low temperature is a technically simple high yield route to TMSCCl2Br. The latter is a stable source of the dichlorobromomethide carbanion, which undergoes 1,4-addition with cyclic nitroalkenes and (E)-fumarates leading to dichlorocyclopropanes after bromide explusion. For nitrostyrenes the reaction arrests at the 1,4-addition product. Low temperature NMR studies and DFT calculations suggest the formation of an ‘ate’ species [(nitronate)SiFMe3]- which, upon boil off of TMSF at 10 - 20 °C, yields the cyclopropane. DFT calculations also support the experimental differences between fluoride and acetate as promotors. |
| first_indexed | 2025-11-14T19:17:45Z |
| format | Article |
| id | nottingham-32995 |
| institution | University of Nottingham Malaysia Campus |
| institution_category | Local University |
| last_indexed | 2025-11-14T19:17:45Z |
| publishDate | 2016 |
| publisher | Wiley-VCH Verlag |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | nottingham-329952020-05-04T17:45:01Z https://eprints.nottingham.ac.uk/32995/ Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes Lee, Darren S. Durán-Peña, Maria Jesus Burroughs, Laurence Woodward, Simon The reaction of excess TMSCl and LiCCl2Br at low temperature is a technically simple high yield route to TMSCCl2Br. The latter is a stable source of the dichlorobromomethide carbanion, which undergoes 1,4-addition with cyclic nitroalkenes and (E)-fumarates leading to dichlorocyclopropanes after bromide explusion. For nitrostyrenes the reaction arrests at the 1,4-addition product. Low temperature NMR studies and DFT calculations suggest the formation of an ‘ate’ species [(nitronate)SiFMe3]- which, upon boil off of TMSF at 10 - 20 °C, yields the cyclopropane. DFT calculations also support the experimental differences between fluoride and acetate as promotors. Wiley-VCH Verlag 2016-04-26 Article PeerReviewed Lee, Darren S., Durán-Peña, Maria Jesus, Burroughs, Laurence and Woodward, Simon (2016) Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes. Chemistry - a European Journal, 2016 (22). ISSN 1521-3765 Dichlorocyclopropane Michael Addition Cyclopropanation Conjugate Addition Cyclopropane http://onlinelibrary.wiley.com/doi/10.1002/chem.201600607/full doi:10.1002/chem.201600607 doi:10.1002/chem.201600607 |
| spellingShingle | Dichlorocyclopropane Michael Addition Cyclopropanation Conjugate Addition Cyclopropane Lee, Darren S. Durán-Peña, Maria Jesus Burroughs, Laurence Woodward, Simon Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes |
| title | Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes |
| title_full | Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes |
| title_fullStr | Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes |
| title_full_unstemmed | Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes |
| title_short | Efficient preparation of TMSCCl2Br and its use in dichlorocyclopropanation of electron deficient alkenes |
| title_sort | efficient preparation of tmsccl2br and its use in dichlorocyclopropanation of electron deficient alkenes |
| topic | Dichlorocyclopropane Michael Addition Cyclopropanation Conjugate Addition Cyclopropane |
| url | https://eprints.nottingham.ac.uk/32995/ https://eprints.nottingham.ac.uk/32995/ https://eprints.nottingham.ac.uk/32995/ |