Chromium Compounds with CO or Isocyanides

McGlinchey, Michael J.; Ortin, Yannick; Seward, Corey

doi:10.1016/b0-08-045047-4/00069-8

Cited by 3 publications

(2 citation statements)

References 630 publications

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“…Transition metal based dearomatization reactions have been intensively developed starting from arenes coordinated either in a hexahapto fashion or in a dihapto one. The first methodology involves electrophilic η 6 -arenes coordinated to Cr(CO) 3 , Mn(CO) 3 , − , RuCp, and FeCp (Cp = cyclopentadienyl). Here we focus on dearomatization of arene−metal giving cyclohexadienes derivatives.…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of (η⁵-Hydroxyalkylcyclohexadienyl)Mn(CO)₃ Complexes

et al. 2010

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Hydroxyalkylcyclohexadienyl)tricarbonylmanganese complexes 3a and 3b have been prepared, and their rearomatization delivered compounds 5 and 6, the first benzylic alcohol derivatives coordinated to the cationic Mn(CO) 3 tripod. The structure of 5 has been determined by X-ray crystallography. 1-Hydroxyalkyl 3a, 7, 8, 2-hydroxyalkyl 19, 20, and 3-hydroxyalkyl 25, 26 (η 5cyclohexadienyl)tricarbonylmanganese complexes have been synthesized and studied toward trifluoroacetylation of the hydroxy group when submitted to the action of NEt 3 and (CF 3 CO) 2 O. Only the 2hydroxyalkyl-substituted complexes eclipsed by a Mn-CO bond of the Mn(CO) 3 tripod gave the expected trifluoroacetate derivatives 21 and 22. For the 1-hydroxyalkyl-substituted complexes, elimination of the trifluoroacetoxy group took place followed by decoordination of the Mn(CO) 3 moiety and trifluoroacetylation, giving rise to trifluoromethyltrienones 10, 11, and 12, whose stuctures were established by X-ray analysis. For 3-hydroxyalkyl-substituted complexes, elimination of the trifluoroacetoxy group also occurred, yielding free arenes 27 and 28 by decoordination of the Mn(CO) 3 entity.

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Section: Resultsmentioning

confidence: 99%

Synthesis and Reactivity of (η⁵-Hydroxyalkylcyclohexadienyl)Mn(CO)₃ Complexes

et al. 2010

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“…Arenes coordinated to transition metals represent a well-established class of organometallic compounds . For application to organic synthesis in particular, chromium − and manganese , complexes have been intensively investigated over the years, and their chemistry is well-known and developed. However, reports on heterobimetallic chromium−manganese complexes are still quite rare so far, although heterobimetallic compounds have received considerable attention, since they allow detailed studies of a potential interaction or cooperation of both metal moieties, which may result in a tuning of individual metal properties …”

Section: Introductionmentioning

confidence: 99%

Heterobimetallic Cr−Mn Complexes of Fused Arenes: Chromium-Templated Benzannulation of a Cymanthrene-Type Metal Carbene and Haptotropic Metal Migration along a Dibenzo[c,e]indene Platform

et al. 2009

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The chromium-templated benzannulation of the chromium cymanthrene-type carbene 3 with 3-hexyne affords the heterobimetallic chromium−manganese hydroquinoid dibenzo[c,e]indene complexes anti-4 and syn-5, in which the chromium entities are coordinated regioselectively to the hydroquinoid ring. Both diastereomers undergo a thermoinduced haptotropic migration of the chromium moiety to give their haptotropomers anti-6 and syn-7 in comparable yields, independent of the relative configuration of both metal centers, while the manganese fragment remains coordinated to the cyclopentadienyl ring. The molecular structures of all heterobimetallic complex structures were established by X-ray analysis. A kinetic NMR study of the chromium migration revealed first-order kinetics for the anti complex 4, supporting the intramolecular nature of the metal rearrangement.

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Resolution of Planar Chiral Cationic (η⁶-Arene)tricarbonylmanganese Complexes

2009

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This contribution describes the first resolution of cationic (eta(6)-arene)Mn(CO)(3) complexes through addition of d-(+)-camphor enolate, isomerization of the stereogenic center, and separation and recrystallization of the corresponding eta(5) diastereoisomers followed by rearomatization and elimination of the chiral auxiliary. This general unprecedented chiral nucleophile addition/elimination (eta(6)-eta(5))/(eta(5)-eta(6)) "round trip" sequence uses a cheap, commercially available chiral nucleophile. As it is compatible with the presence of halide and alkoxy groups, a huge number of applications are envisaged. Some of them, such as the synthesis of enantiopure substituted cyclohexenones, are reported in the present work.

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Chromium Compounds with CO or Isocyanides

Cited by 3 publications

References 630 publications

Synthesis and Reactivity of (η⁵-Hydroxyalkylcyclohexadienyl)Mn(CO)₃ Complexes

Synthesis and Reactivity of (η⁵-Hydroxyalkylcyclohexadienyl)Mn(CO)₃ Complexes

Heterobimetallic Cr−Mn Complexes of Fused Arenes: Chromium-Templated Benzannulation of a Cymanthrene-Type Metal Carbene and Haptotropic Metal Migration along a Dibenzo[c,e]indene Platform

Resolution of Planar Chiral Cationic (η⁶-Arene)tricarbonylmanganese Complexes

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Chromium Compounds with CO or Isocyanides

Cited by 3 publications

References 630 publications

Synthesis and Reactivity of (η5-Hydroxyalkylcyclohexadienyl)Mn(CO)3 Complexes

Synthesis and Reactivity of (η5-Hydroxyalkylcyclohexadienyl)Mn(CO)3 Complexes

Heterobimetallic Cr−Mn Complexes of Fused Arenes: Chromium-Templated Benzannulation of a Cymanthrene-Type Metal Carbene and Haptotropic Metal Migration along a Dibenzo[c,e]indene Platform

Resolution of Planar Chiral Cationic (η6-Arene)tricarbonylmanganese Complexes

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Synthesis and Reactivity of (η⁵-Hydroxyalkylcyclohexadienyl)Mn(CO)₃ Complexes

Synthesis and Reactivity of (η⁵-Hydroxyalkylcyclohexadienyl)Mn(CO)₃ Complexes

Resolution of Planar Chiral Cationic (η⁶-Arene)tricarbonylmanganese Complexes