Academic Journal
The chlorinating behaviour of WCl6 towards α-aminoacids
| العنوان: | The chlorinating behaviour of WCl6 towards α-aminoacids |
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| المؤلفون: | Bortoluzzi, Marco, MARCHETTI, FABIO, Murrali, Maria Grazia, PAMPALONI, GUIDO, Zacchini, Stefano |
| المساهمون: | Bortoluzzi, Marco, Marchetti, Fabio, Murrali, Maria Grazia, Pampaloni, Guido, Zacchini, Stefano |
| سنة النشر: | 2015 |
| المجموعة: | ARPI - Archivio della Ricerca dell'Università di Pisa |
| مصطلحات موضوعية: | EFFECTIVE CORE POTENTIALS, X-RAY-STRUCTURE, CRYSTAL-STRUCTURE, MOLECULAR CALCULATIONS, PROLINE HYDROCHLORIDE, HYDROGEN-BONDS, COMPLEXES, SARCOSINE, CHEMISTRY, 2,5-DIKETOPIPERAZINES |
| الوصف: | Cl/O interchange took place when WCl6 was allowed to interact with a series of α-aminoacids. The α-ammonium-acylchloride salts [NH2(CH2)3CHC(O)Cl][WOCl5], 1a, and [MeNH2CH2C(O)Cl][WOCl5], 1b, were afforded in ca. 55% yields from the reactions of WCl6 with, respectively, L-proline and sarcosine in CH2Cl2. By using other reaction media (hexane or CHCl3), the α-amino-acylchloride complexes WOCl4[O[double bond, length as m-dash]C(Cl)CH(CH2)3NH2], 5a, and WOCl4[O[double bond, length as m-dash]C(Cl)CH(R)NHR′] (R = H, R′ = Me, 5b; R = R′ = H, 5c; R = Me, R′ = H, 5d) were isolated in moderate to good yields from WCl6 and, respectively, L-proline, sarcosine, glycine and L-alanine. The formation of 5a,b is basically the result of HCl release from the parent compounds 1a,b. 5a represents a key intermediate in the course of the reaction leading to (WOCl4)2[μ:κ2(O)-dkp], 2, dkp = (S,S)-octahydrodipyrrolo[1,2-a:1′,2′-d]pyrazine-5,10-dione. 2 was optimally prepared from WCl6/L-proline under high temperature conditions. Hydrolytic treatment of 2 afforded the L-proline-derived 2,5-diketopiperazine (dkp), which was finally isolated with an overall yield of 70%. 1a,b were characterized by X-ray diffractometry, thus providing very rare examples of crystallographically characterized acylchloride derivatives of α-aminoacids. DFT calculations were extensively carried out in order to shed light on structural and mechanistic features. |
| نوع الوثيقة: | article in journal/newspaper |
| وصف الملف: | STAMPA |
| اللغة: | English |
| Relation: | info:eu-repo/semantics/altIdentifier/pmid/25858790; info:eu-repo/semantics/altIdentifier/wos/WOS:000353643300042; volume:44; issue:18; firstpage:8729; lastpage:8738; numberofpages:10; journal:DALTON TRANSACTIONS; http://hdl.handle.net/11568/754719; info:eu-repo/semantics/altIdentifier/scopus/2-s2.0-84928962827; http://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt00518c#!divAbstract |
| DOI: | 10.1039/c5dt00518c |
| الاتاحة: | http://hdl.handle.net/11568/754719 https://doi.org/10.1039/c5dt00518c http://pubs.rsc.org/en/content/articlelanding/2015/dt/c5dt00518c#!divAbstract |
| Rights: | info:eu-repo/semantics/openAccess |
| رقم الانضمام: | edsbas.180941EA |
| قاعدة البيانات: | BASE |
| DOI: | 10.1039/c5dt00518c |
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