File Download

There are no files associated with this item.

  Links for fulltext
     (May Require Subscription)
Supplementary

Article: Cis-β-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanation

TitleCis-β-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanation
Authors
Issue Date2009
PublisherAmerican 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?
Abstractcis-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 Identifierhttp://hdl.handle.net/10722/168394
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorXu, ZJen_HK
dc.contributor.authorFang, Ren_HK
dc.contributor.authorZhao, Cen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorLi, GYen_HK
dc.contributor.authorZhu, Nen_HK
dc.contributor.authorChe, CMen_HK
dc.date.accessioned2012-10-08T03:18:24Z-
dc.date.available2012-10-08T03:18:24Z-
dc.date.issued2009en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2009, v. 131 n. 12, p. 4405-4417en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/168394-
dc.description.abstractcis-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.languageengen_US
dc.publisherAmerican Chemical Society. The Journal's web site is located at http://pubs.acs.org/journals/jacsat/index.htmlen_HK
dc.relation.ispartofJournal of the American Chemical Societyen_HK
dc.titleCis-β-bis(carbonyl) ruthenium-salen complexes: X-ray crystal structures and remarkable catalytic properties toward asymmetric intramolecular alkene cyclopropanationen_HK
dc.typeArticleen_HK
dc.identifier.emailHuang, JS: jshuang@hku.hken_HK
dc.identifier.emailZhu, N: nzhu@hkucc.hku.hken_HK
dc.identifier.emailChe, CM: cmche@hku.hken_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.identifier.authorityZhu, N=rp00845en_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.description.naturelink_to_subscribed_fulltexten_US
dc.identifier.doi10.1021/ja8086399en_HK
dc.identifier.pmid19275149-
dc.identifier.scopuseid_2-s2.0-67849105121en_HK
dc.identifier.hkuros155742-
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-67849105121&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume131en_HK
dc.identifier.issue12en_HK
dc.identifier.spage4405en_HK
dc.identifier.epage4417en_HK
dc.identifier.eissn1520-5126-
dc.identifier.isiWOS:000264792900051-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridXu, ZJ=8708548900en_HK
dc.identifier.scopusauthoridFang, R=10144173000en_HK
dc.identifier.scopusauthoridZhao, C=7403563836en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridLi, GY=15765581300en_HK
dc.identifier.scopusauthoridZhu, N=7201449530en_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK

Export via OAI-PMH Interface in XML Formats


OR


Export to Other Non-XML Formats