The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives
The preparation of a series of diastereoisomeric tetracamphorsulfonates derived from racemic tetramethoxyresorcin[4]arenes was achieved by reactions with an excess of (S)‐(+)‐10‐camphorsulfonyl chloride in pyridine followed by isolation using flash chromatography. Tetradeprotonation of a number of t...
| Main Authors: | , , , , , , , , , , , |
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| Format: | Journal Article |
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Wiley-VCH Verlag GMBH
2006
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| Online Access: | http://hdl.handle.net/20.500.11937/42136 |
| _version_ | 1848756337126670336 |
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| author | Buckley, B. Page, P. Chan, Y. Heaney, H. Klaes, M. Mcildowie, M. McKee, V. Mattay, J. Mocerino, Mauro Moreno, E. Skelton, B. White, A. |
| author_facet | Buckley, B. Page, P. Chan, Y. Heaney, H. Klaes, M. Mcildowie, M. McKee, V. Mattay, J. Mocerino, Mauro Moreno, E. Skelton, B. White, A. |
| author_sort | Buckley, B. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | The preparation of a series of diastereoisomeric tetracamphorsulfonates derived from racemic tetramethoxyresorcin[4]arenes was achieved by reactions with an excess of (S)‐(+)‐10‐camphorsulfonyl chloride in pyridine followed by isolation using flash chromatography. Tetradeprotonation of a number of tetramethoxyresorcin[4]arenes using n‐butyllithium in tetrahydrofuran, followed by reactions using (S)‐(+)‐10‐camphorsulfonyl chloride, gave the same tetracamphorsulfonates. Mono‐, di‐ and tricamphorsulfonates were also prepared following selective deprotonation. In the reactions with tetraisopropyloxy‐ and tetracyclopentyloxyresorcin[4]arenes, only the mono‐ and dicamphorsulfonates were formed. X‐ray crystallographic analysis established the absolute configurations of three diastereoisomerically pure tetracamphorsulfonates, including a diastereoisomer prepared from 6,12,18,24‐tetramethoxy‐2,8,14,20‐tetrakis(2‐methylpropyl)resorcin[4]arene. An additional pair of diastereoisomers was also prepared using (R)‐(–)‐10‐camphorsulfonyl chloride and 6,12,18,24‐tetramethoxy‐2,8,14,20‐tetrakis(2‐methylpropyl)resorcin[4]arene, for one of which the structure was confirmed by an additional X‐ray structure determination. Hydrolytic removal of the camphorsulfonyl residue(s) from the various diastereoisomers gave enantiomers of known absolute configurations. In some cases, the chiral nonracemic tetraalkoxyresorcin[4]arenes were converted into known tetrabenzoxazine derivatives by using N,N‐bis(methoxymethyl)[(S)‐(–)‐(α‐methylbenzyl)]amine in thermal or microwave‐assisted reactions. |
| first_indexed | 2025-11-14T09:10:35Z |
| format | Journal Article |
| id | curtin-20.500.11937-42136 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T09:10:35Z |
| publishDate | 2006 |
| publisher | Wiley-VCH Verlag GMBH |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-421362019-05-17T01:48:34Z The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives Buckley, B. Page, P. Chan, Y. Heaney, H. Klaes, M. Mcildowie, M. McKee, V. Mattay, J. Mocerino, Mauro Moreno, E. Skelton, B. White, A. - Hydrolysis Resorcin[4]arenes Configuration determination Chiral auxiliaries Axial chirality Mannich reactions Camphorsulfonates Diastereoselectivity The preparation of a series of diastereoisomeric tetracamphorsulfonates derived from racemic tetramethoxyresorcin[4]arenes was achieved by reactions with an excess of (S)‐(+)‐10‐camphorsulfonyl chloride in pyridine followed by isolation using flash chromatography. Tetradeprotonation of a number of tetramethoxyresorcin[4]arenes using n‐butyllithium in tetrahydrofuran, followed by reactions using (S)‐(+)‐10‐camphorsulfonyl chloride, gave the same tetracamphorsulfonates. Mono‐, di‐ and tricamphorsulfonates were also prepared following selective deprotonation. In the reactions with tetraisopropyloxy‐ and tetracyclopentyloxyresorcin[4]arenes, only the mono‐ and dicamphorsulfonates were formed. X‐ray crystallographic analysis established the absolute configurations of three diastereoisomerically pure tetracamphorsulfonates, including a diastereoisomer prepared from 6,12,18,24‐tetramethoxy‐2,8,14,20‐tetrakis(2‐methylpropyl)resorcin[4]arene. An additional pair of diastereoisomers was also prepared using (R)‐(–)‐10‐camphorsulfonyl chloride and 6,12,18,24‐tetramethoxy‐2,8,14,20‐tetrakis(2‐methylpropyl)resorcin[4]arene, for one of which the structure was confirmed by an additional X‐ray structure determination. Hydrolytic removal of the camphorsulfonyl residue(s) from the various diastereoisomers gave enantiomers of known absolute configurations. In some cases, the chiral nonracemic tetraalkoxyresorcin[4]arenes were converted into known tetrabenzoxazine derivatives by using N,N‐bis(methoxymethyl)[(S)‐(–)‐(α‐methylbenzyl)]amine in thermal or microwave‐assisted reactions. 2006 Journal Article http://hdl.handle.net/20.500.11937/42136 10.1002/ejoc.200600591 Wiley-VCH Verlag GMBH fulltext |
| spellingShingle | - Hydrolysis Resorcin[4]arenes Configuration determination Chiral auxiliaries Axial chirality Mannich reactions Camphorsulfonates Diastereoselectivity Buckley, B. Page, P. Chan, Y. Heaney, H. Klaes, M. Mcildowie, M. McKee, V. Mattay, J. Mocerino, Mauro Moreno, E. Skelton, B. White, A. The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives |
| title | The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives |
| title_full | The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives |
| title_fullStr | The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives |
| title_full_unstemmed | The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives |
| title_short | The Preparation and Absolute Configurations of Enantiomerically Pure C4-Symmetric Tetraalkoxyresorcin[4]arenes Obtained from Camphorsulfonate Derivatives |
| title_sort | preparation and absolute configurations of enantiomerically pure c4-symmetric tetraalkoxyresorcin[4]arenes obtained from camphorsulfonate derivatives |
| topic | - Hydrolysis Resorcin[4]arenes Configuration determination Chiral auxiliaries Axial chirality Mannich reactions Camphorsulfonates Diastereoselectivity |
| url | http://hdl.handle.net/20.500.11937/42136 |