Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive
The addition of organocuprates to α,β-unsaturated substrates, namely E-cinamaldehyde and 2-cyclohexen-1-one, was studied in THF. The furan moiety was chosen for the heterocuprate, because the methods for the synthesis of furan derivatives are scarce and they have a strong potentiality for tandem rea...
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| Acceso en línea: | http://hdl.handle.net/20.500.12110/paper_1551-701_v2008_n6_p140_Rodriguez |
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todo:paper_1551-701_v2008_n6_p140_Rodriguez2023-10-03T16:25:18Z Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive Rodríguez, C. Vázquez, Á. Nudelman, N.S. Conjugated addition Furyllithium Organocuprates TMSCl α,β- unsaturated carbonyl compound The addition of organocuprates to α,β-unsaturated substrates, namely E-cinamaldehyde and 2-cyclohexen-1-one, was studied in THF. The furan moiety was chosen for the heterocuprate, because the methods for the synthesis of furan derivatives are scarce and they have a strong potentiality for tandem reactions. The performance of CuBr; CuBr.SMe2 and CuCN as copper precursors was examined: the higher yields of the 1,4-addition product were obtained using CuCN. The reaction with 2-cyclohexen-1-one gave the best results. In some cases, a compound that arises from dehydration of the 1,2-addition product was obtained and its yield increases near 70% when the reaction is carried out with furyl-lithium in the absence of any copper salt. Addition of up to 6 equivalents of TMSCl to the reaction mixture of 2-cyclohexen-1-one with furylcuprate at -78 C, leads to a clean addition yielding more than 90% of the 1,4-addition product. The only by-product is 2-TMS-furan. The absence of silylated ether of the enolate, is a strong evidence to rule out the cyclic intermediate or transition state that was previously proposed as the mechanism whereby TMSCl (acting as a Lewis base toward the cuprate) accelerates the reaction. Promoting conversion of the initially formed π-complex to a reactive tetravalent copper species is proposed instead. ©ARKAT-USA, Inc. Fil:Vázquez, Á. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_1551-701_v2008_n6_p140_Rodriguez |
| institution |
Universidad de Buenos Aires |
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I-28 |
| repository_str |
R-134 |
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
Conjugated addition Furyllithium Organocuprates TMSCl α,β- unsaturated carbonyl compound |
| spellingShingle |
Conjugated addition Furyllithium Organocuprates TMSCl α,β- unsaturated carbonyl compound Rodríguez, C. Vázquez, Á. Nudelman, N.S. Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive |
| topic_facet |
Conjugated addition Furyllithium Organocuprates TMSCl α,β- unsaturated carbonyl compound |
| description |
The addition of organocuprates to α,β-unsaturated substrates, namely E-cinamaldehyde and 2-cyclohexen-1-one, was studied in THF. The furan moiety was chosen for the heterocuprate, because the methods for the synthesis of furan derivatives are scarce and they have a strong potentiality for tandem reactions. The performance of CuBr; CuBr.SMe2 and CuCN as copper precursors was examined: the higher yields of the 1,4-addition product were obtained using CuCN. The reaction with 2-cyclohexen-1-one gave the best results. In some cases, a compound that arises from dehydration of the 1,2-addition product was obtained and its yield increases near 70% when the reaction is carried out with furyl-lithium in the absence of any copper salt. Addition of up to 6 equivalents of TMSCl to the reaction mixture of 2-cyclohexen-1-one with furylcuprate at -78 C, leads to a clean addition yielding more than 90% of the 1,4-addition product. The only by-product is 2-TMS-furan. The absence of silylated ether of the enolate, is a strong evidence to rule out the cyclic intermediate or transition state that was previously proposed as the mechanism whereby TMSCl (acting as a Lewis base toward the cuprate) accelerates the reaction. Promoting conversion of the initially formed π-complex to a reactive tetravalent copper species is proposed instead. ©ARKAT-USA, Inc. |
| format |
JOUR |
| author |
Rodríguez, C. Vázquez, Á. Nudelman, N.S. |
| author_facet |
Rodríguez, C. Vázquez, Á. Nudelman, N.S. |
| author_sort |
Rodríguez, C. |
| title |
Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive |
| title_short |
Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive |
| title_full |
Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive |
| title_fullStr |
Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive |
| title_full_unstemmed |
Conjugate additions of furylcuprates to α-enones. The effect of the copper precursor and of TMSCl used as additive |
| title_sort |
conjugate additions of furylcuprates to α-enones. the effect of the copper precursor and of tmscl used as additive |
| url |
http://hdl.handle.net/20.500.12110/paper_1551-701_v2008_n6_p140_Rodriguez |
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1807318626074624000 |