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Article: Asymmetric inter- and intramolecular cyclopropanation of alkenes catalyzed by chiral ruthenium porphyrins. Synthesis and crystal structure of a chiral metalloporphyrin carbene complex

TitleAsymmetric inter- and intramolecular cyclopropanation of alkenes catalyzed by chiral ruthenium porphyrins. Synthesis and crystal structure of a chiral metalloporphyrin carbene complex
Authors
Issue Date2001
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, 2001, v. 123 n. 18, p. 4119-4129 How to Cite?
AbstractExtensive investigations of asymmetric intermolecular cyclopropanation of terminal alkenes with diazoacetates catalyzed by ruthenium porphyrin [Ru(P*)(CO)(EtOH)] (1, H 2P* = 5,10,15,20-tetrakis-{(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8- dimethanoanthracene-9-yl}porphyrin) and the application of catalyst 1 to asymmetric intramolecular cyclopropanation of allylic or homoallylic diazoacetates are described. The intermolecular cyclopropanation of styrene and its derivatives with ethyl diazoacetate afforded the corresponding cyclopropyl esters in up to 98% ee with high trans/cis ratios of up to 36 and extremely high catalyst turnovers of up to 1.1 × 10 4. Examination of the effects of temperature, diazoacetate, solvent, and substituent in the intermolecular cyclopropanation reveals that (i) both enantioselectivity and trans selectivity increase with decreasing temperature, (ii) sterically encumbered diazoacetates N 2CHCO 2R such as R = Bu t, and donor solvents, such as diethyl ether and tetrahydrofuran, are beneficial to the trans selectivity, and (iii) electron-donating para substituents on styrene accelerate the cyclopropanations, with the log(k x/k H) vs σ + plot for para-substituted styrenes p-X-C 6H 4CH=CH 2 (X = MeO, Me, Cl, CF 3) exhibiting good linearity with a small negative ρ + value of -0.44 ± 0.09. In the case of intramolecular cyclopropanation, complex 1 promoted the decomposition of a series of allylic diazoacetates to form the cyclopropyl lactones in up to 85% ee, contributing the first efficient metalloporphyrin catalyst for an asymmetric intramolecular cyclopropanation. Both the inter- and intramolecular cyclopropanations were proposed to proceed via a reactive chiral ruthenium carbene intermediate. The enantioselectivities in these processes were rationalized on the basis of the X-ray crystal structures of closely related stable chiral carbene complexes [Ru(P*)(CPh 2)] (2) and [Ru(P*)(C(Ph)-CO 2CH 2CH=CH 2)] (3) obtained from reactions of complex 1 with N 2CPh 2 and N 2C(Ph)CO 2CH 2CH=CH 2, respectively.
Persistent Identifierhttp://hdl.handle.net/10722/69057
ISSN
2015 Impact Factor: 13.038
2015 SCImago Journal Rankings: 7.123
ISI Accession Number ID
References

 

DC FieldValueLanguage
dc.contributor.authorChe, CMen_HK
dc.contributor.authorHuang, JSen_HK
dc.contributor.authorLee, FWen_HK
dc.contributor.authorLi, Yen_HK
dc.contributor.authorLai, TSen_HK
dc.contributor.authorKwong, HLen_HK
dc.contributor.authorTeng, PFen_HK
dc.contributor.authorLee, WSen_HK
dc.contributor.authorLo, WCen_HK
dc.contributor.authorPeng, SMen_HK
dc.contributor.authorZhou, ZYen_HK
dc.date.accessioned2010-09-06T06:10:09Z-
dc.date.available2010-09-06T06:10:09Z-
dc.date.issued2001en_HK
dc.identifier.citationJournal Of The American Chemical Society, 2001, v. 123 n. 18, p. 4119-4129en_HK
dc.identifier.issn0002-7863en_HK
dc.identifier.urihttp://hdl.handle.net/10722/69057-
dc.description.abstractExtensive investigations of asymmetric intermolecular cyclopropanation of terminal alkenes with diazoacetates catalyzed by ruthenium porphyrin [Ru(P*)(CO)(EtOH)] (1, H 2P* = 5,10,15,20-tetrakis-{(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8- dimethanoanthracene-9-yl}porphyrin) and the application of catalyst 1 to asymmetric intramolecular cyclopropanation of allylic or homoallylic diazoacetates are described. The intermolecular cyclopropanation of styrene and its derivatives with ethyl diazoacetate afforded the corresponding cyclopropyl esters in up to 98% ee with high trans/cis ratios of up to 36 and extremely high catalyst turnovers of up to 1.1 × 10 4. Examination of the effects of temperature, diazoacetate, solvent, and substituent in the intermolecular cyclopropanation reveals that (i) both enantioselectivity and trans selectivity increase with decreasing temperature, (ii) sterically encumbered diazoacetates N 2CHCO 2R such as R = Bu t, and donor solvents, such as diethyl ether and tetrahydrofuran, are beneficial to the trans selectivity, and (iii) electron-donating para substituents on styrene accelerate the cyclopropanations, with the log(k x/k H) vs σ + plot for para-substituted styrenes p-X-C 6H 4CH=CH 2 (X = MeO, Me, Cl, CF 3) exhibiting good linearity with a small negative ρ + value of -0.44 ± 0.09. In the case of intramolecular cyclopropanation, complex 1 promoted the decomposition of a series of allylic diazoacetates to form the cyclopropyl lactones in up to 85% ee, contributing the first efficient metalloporphyrin catalyst for an asymmetric intramolecular cyclopropanation. Both the inter- and intramolecular cyclopropanations were proposed to proceed via a reactive chiral ruthenium carbene intermediate. The enantioselectivities in these processes were rationalized on the basis of the X-ray crystal structures of closely related stable chiral carbene complexes [Ru(P*)(CPh 2)] (2) and [Ru(P*)(C(Ph)-CO 2CH 2CH=CH 2)] (3) obtained from reactions of complex 1 with N 2CPh 2 and N 2C(Ph)CO 2CH 2CH=CH 2, respectively.en_HK
dc.languageengen_HK
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.titleAsymmetric inter- and intramolecular cyclopropanation of alkenes catalyzed by chiral ruthenium porphyrins. Synthesis and crystal structure of a chiral metalloporphyrin carbene complexen_HK
dc.typeArticleen_HK
dc.identifier.openurlhttp://library.hku.hk:4550/resserv?sid=HKU:IR&issn=0002-7863&volume=123&spage=4119&epage=4129&date=2001&atitle=Asymmetric+Inter-+and+Intramolecular+Cyclopropanation+of+Alkenes+Catalyzed+by+Chiral+Ruthenium+Porphyrins.++Synthesis+and+Crystal+Structure+of+a+Chiral+Metalloporphyrin+Carbene+Complexen_HK
dc.identifier.emailChe, CM:cmche@hku.hken_HK
dc.identifier.emailHuang, JS:jshuang@hkucc.hku.hken_HK
dc.identifier.authorityChe, CM=rp00670en_HK
dc.identifier.authorityHuang, JS=rp00709en_HK
dc.description.naturelink_to_subscribed_fulltext-
dc.identifier.doi10.1021/ja001416fen_HK
dc.identifier.pmid11457174-
dc.identifier.scopuseid_2-s2.0-0034794315en_HK
dc.identifier.hkuros62308en_HK
dc.relation.referenceshttp://www.scopus.com/mlt/select.url?eid=2-s2.0-0034794315&selection=ref&src=s&origin=recordpageen_HK
dc.identifier.volume123en_HK
dc.identifier.issue18en_HK
dc.identifier.spage4119en_HK
dc.identifier.epage4129en_HK
dc.identifier.isiWOS:000168495800002-
dc.publisher.placeUnited Statesen_HK
dc.identifier.scopusauthoridChe, CM=7102442791en_HK
dc.identifier.scopusauthoridHuang, JS=7407192639en_HK
dc.identifier.scopusauthoridLee, FW=7403111574en_HK
dc.identifier.scopusauthoridLi, Y=35187394200en_HK
dc.identifier.scopusauthoridLai, TS=7202203490en_HK
dc.identifier.scopusauthoridKwong, HL=35569416300en_HK
dc.identifier.scopusauthoridTeng, PF=7006192221en_HK
dc.identifier.scopusauthoridLee, WS=46361348400en_HK
dc.identifier.scopusauthoridLo, WC=36923786500en_HK
dc.identifier.scopusauthoridPeng, SM=35464852200en_HK
dc.identifier.scopusauthoridZhou, ZY=46361942000en_HK

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