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Article: Cis-β-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanation
Title | Cis-β-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanation |
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Authors | |
Issue Date | 2009 |
Publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html |
Citation | Journal Of The American Chemical Society, 2009, v. 131 n. 12, p. 4405-4417 How to Cite? |
Abstract | cis-β-[Ru"(salen A)(CO) 2] (salen A = N,N-bis(3-R 1-5-R 2-salicylidene)-1,2-cyclohexenediamine di- anion; R 1 = R 2 = Bu t, 1a;R 1 = Pr t,R 2 = H, 1b;R 1 = Bu t,R 2 = H, 1c) complexes were prepared by treating Ru 3(CO) 12 with the respective H 2salen A in 1,2,4-trichlorobenzene and structurally characterized by X-ray crystallography. Complexes 1a-c catalyze intramolecular cyclopropanation of trans-allylic diazoacetates N 2CHCO 2CH 2CH=CHR (3,R = Ph, 4-ClC 6H 4, 4-BrC 6H 4, 4-MeC 6H 4, 4-MeOC 6H 4, 2-MeC 6H 4, 2-furanyl) under light irradiation to give cyclopropyl lactones 4 in up to 96% yield and up to 98% ee. DFT calculations on intramolecular cyclopropanation of 3a (R = Ph) with model catalyst cis-β-[Ru ll(salen A0)(CO) 2] (salen A0 = N, N-bis(salicylidene)-1,2-cyclohexenediamine dianion) reveal the intermediacy of both cis-β- and trans- [Ru(salen A0) (CHCO 2CH2CH=CHPh)(CO)] bearing salen A0 in a nonplanar and planar coordination mode, respectively, with the cis-β-carbene species being a major intermediate in the catalytic carbenoid transfer reaction. The intramolecular cyclopropanation from the cis-β-carbene species is the most favorable pathway and features an early transition state and an asynchronous concerted [2 + 1] addition mechanism. Enantioselectivities in the reactions involving [Ru(salen A0)(CHCO 2CH 2CH=CHPh)(CO)] were predicted to be 77% ee for the trans-carbene species and 96% ee for the cis-p-carbene species; the former dramatically increases to 98% ee, whereas the latter slightly increases to 99% ee, upon replacing salen A0 with salen A1 (R 1 = R 2 = B t). The observed variation in enantioselectivity (90-98% ee) for the conversion of 3a to 4a catalyzed by 1a-c could result from an equilibrium between cis-β (major) and tans (minor) ruthenium-carbene intermediates. © 2009 American Chemical Society. |
Persistent Identifier | http://hdl.handle.net/10722/168394 |
ISSN | 2023 Impact Factor: 14.4 2023 SCImago Journal Rankings: 5.489 |
ISI Accession Number ID | |
References |
DC Field | Value | Language |
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dc.contributor.author | Xu, ZJ | en_HK |
dc.contributor.author | Fang, R | en_HK |
dc.contributor.author | Zhao, C | en_HK |
dc.contributor.author | Huang, JS | en_HK |
dc.contributor.author | Li, GY | en_HK |
dc.contributor.author | Zhu, N | en_HK |
dc.contributor.author | Che, CM | en_HK |
dc.date.accessioned | 2012-10-08T03:18:24Z | - |
dc.date.available | 2012-10-08T03:18:24Z | - |
dc.date.issued | 2009 | en_HK |
dc.identifier.citation | Journal Of The American Chemical Society, 2009, v. 131 n. 12, p. 4405-4417 | en_HK |
dc.identifier.issn | 0002-7863 | en_HK |
dc.identifier.uri | http://hdl.handle.net/10722/168394 | - |
dc.description.abstract | cis-β-[Ru"(salen A)(CO) 2] (salen A = N,N-bis(3-R 1-5-R 2-salicylidene)-1,2-cyclohexenediamine di- anion; R 1 = R 2 = Bu t, 1a;R 1 = Pr t,R 2 = H, 1b;R 1 = Bu t,R 2 = H, 1c) complexes were prepared by treating Ru 3(CO) 12 with the respective H 2salen A in 1,2,4-trichlorobenzene and structurally characterized by X-ray crystallography. Complexes 1a-c catalyze intramolecular cyclopropanation of trans-allylic diazoacetates N 2CHCO 2CH 2CH=CHR (3,R = Ph, 4-ClC 6H 4, 4-BrC 6H 4, 4-MeC 6H 4, 4-MeOC 6H 4, 2-MeC 6H 4, 2-furanyl) under light irradiation to give cyclopropyl lactones 4 in up to 96% yield and up to 98% ee. DFT calculations on intramolecular cyclopropanation of 3a (R = Ph) with model catalyst cis-β-[Ru ll(salen A0)(CO) 2] (salen A0 = N, N-bis(salicylidene)-1,2-cyclohexenediamine dianion) reveal the intermediacy of both cis-β- and trans- [Ru(salen A0) (CHCO 2CH2CH=CHPh)(CO)] bearing salen A0 in a nonplanar and planar coordination mode, respectively, with the cis-β-carbene species being a major intermediate in the catalytic carbenoid transfer reaction. The intramolecular cyclopropanation from the cis-β-carbene species is the most favorable pathway and features an early transition state and an asynchronous concerted [2 + 1] addition mechanism. Enantioselectivities in the reactions involving [Ru(salen A0)(CHCO 2CH 2CH=CHPh)(CO)] were predicted to be 77% ee for the trans-carbene species and 96% ee for the cis-p-carbene species; the former dramatically increases to 98% ee, whereas the latter slightly increases to 99% ee, upon replacing salen A0 with salen A1 (R 1 = R 2 = B t). The observed variation in enantioselectivity (90-98% ee) for the conversion of 3a to 4a catalyzed by 1a-c could result from an equilibrium between cis-β (major) and tans (minor) ruthenium-carbene intermediates. © 2009 American Chemical Society. | en_HK |
dc.language | eng | en_US |
dc.publisher | American Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.html | en_HK |
dc.relation.ispartof | Journal of the American Chemical Society | en_HK |
dc.title | Cis-β-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanation | en_HK |
dc.type | Article | en_HK |
dc.identifier.email | Huang, JS: jshuang@hku.hk | en_HK |
dc.identifier.email | Zhu, N: nzhu@hkucc.hku.hk | en_HK |
dc.identifier.email | Che, CM: cmche@hku.hk | en_HK |
dc.identifier.authority | Huang, JS=rp00709 | en_HK |
dc.identifier.authority | Zhu, N=rp00845 | en_HK |
dc.identifier.authority | Che, CM=rp00670 | en_HK |
dc.description.nature | link_to_subscribed_fulltext | en_US |
dc.identifier.doi | 10.1021/ja8086399 | en_HK |
dc.identifier.pmid | 19275149 | - |
dc.identifier.scopus | eid_2-s2.0-67849105121 | en_HK |
dc.identifier.hkuros | 155742 | - |
dc.relation.references | http://www.scopus.com/mlt/select.url?eid=2-s2.0-67849105121&selection=ref&src=s&origin=recordpage | en_HK |
dc.identifier.volume | 131 | en_HK |
dc.identifier.issue | 12 | en_HK |
dc.identifier.spage | 4405 | en_HK |
dc.identifier.epage | 4417 | en_HK |
dc.identifier.eissn | 1520-5126 | - |
dc.identifier.isi | WOS:000264792900051 | - |
dc.publisher.place | United States | en_HK |
dc.identifier.scopusauthorid | Xu, ZJ=8708548900 | en_HK |
dc.identifier.scopusauthorid | Fang, R=10144173000 | en_HK |
dc.identifier.scopusauthorid | Zhao, C=7403563836 | en_HK |
dc.identifier.scopusauthorid | Huang, JS=7407192639 | en_HK |
dc.identifier.scopusauthorid | Li, GY=15765581300 | en_HK |
dc.identifier.scopusauthorid | Zhu, N=7201449530 | en_HK |
dc.identifier.scopusauthorid | Che, CM=7102442791 | en_HK |
dc.identifier.issnl | 0002-7863 | - |