Metalation of arenechromium tricarbonyl complexes and electrophilic trapping of the complexed phenyllithium intermediate

Semmelhack, M. F.; Bisaha, John J.; Czarny, Michael R.

doi:10.1021/ja00497a063

Cited by 138 publications

(12 citation statements)

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“…Mass spectra were obtained using In Beam Electron Impact techniques. (4).-A deoxygenated mixture of dibutyl ether (90 ml), THF (9 ml), benzyl alcohol (3.00 g, 27.8 mmol) and hexacarbonylchromium(o) (7.00 g, 31.8 mmol) was heated at reflux (24 h). The cooled solution was filtered and the solvents removed.…”

Section: Discussionmentioning

confidence: 99%

“…Column chromatography (A1203 Grade V, 1 :1, Et,O-light petroleum) of this gave the title compound (13) as a yellow powder (1.51 g, 6673, m.p. 89-91 "C (1it.,l6 90-91.5 "C); v, , , 1 970, 1 940, and 1 900br cm-' (CO); G(CDC13) 5.31-5.22 (m, 4 H, ArH) and 2.17 Tr icarbon y l( q -0 -xy 1ene)ch romium( 0) (1 3) from Tr icarbonyl(q6-benzyl alcohol)chromium(o) (4).-A solution of tricarbonyl(q6-benzyl alcohol)chromium(o) (4) (400 mg, 1.64 mmol) in THF (10 ml) at -78 "C was added dropwise to a mixture of methyl-lithium (2.73 ml, 4.10 mmol) and TMEDA (0.60 ml, 4.00 mmol) in THF (10 ml) at -78 "C. The mixture was allowed to warm to 20 "C and was stirred (3 h). Methanol (2 ml) was added and the mixture evaporated to give a red gum.…”

Section: Tricarandonyl(q6-o-t-butyltoluene)chromium(o)mentioning

confidence: 99%

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Regioselective nucleophilic additions to tricarbonyl(η⁶-arene)chromium(0) complexes: electronic versus chelation control

Blagg¹,

Davies²,

Goodfellow³

et al. 1990

J. Chem. Soc., Perkin Trans. 1

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Section: Discussionmentioning

confidence: 99%

Section: Tricarandonyl(q6-o-t-butyltoluene)chromium(o)mentioning

confidence: 99%

Regioselective nucleophilic additions to tricarbonyl(η⁶-arene)chromium(0) complexes: electronic versus chelation control

Blagg¹,

Davies²,

Goodfellow³

et al. 1990

J. Chem. Soc., Perkin Trans. 1

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“…For example, acylation of o-lithiofluorobenzenetricarbonylchromium with g-butyrolactone at 25 C for 24 h is followed by spontaneous fluoride displacement to give complex 36. Oxidation with excess iodine liberates the lactone in 48 % overall yield (Scheme 15) [20].…”

Section: 21mentioning

confidence: 99%

Arenetricarbonylchromium Complexes: Ipso , Cine , Tele Nucleophilic Aromatic Substitutions

Rose‐Munch

Rose

2002

Modern Arene Chemistry

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The complexation of an arene C 6 H 5 X to the tricarbonylchromium unit promotes addition of nucleophiles to the arene ring due to the strong electron-withdrawing ability of the Cr(CO) 3 group. If addition of the nucleophile Nu occurs at the carbon bearing the leaving group X, this is an overall ipso nucleophilic aromatic substitution S N Ar. If addition of the nucleophile takes place on another carbon, the anionic h 5 -X-cyclohexadienyltricarbonylchromium intermediates can be treated with acid giving h 4 -X-cyclohexadiene derivatives via chromium hydride intermediates. The driving force of these reactions is the elimination of HX. These reactions are called cine and tele S N Ar. In this chapter, an overview of these S N Ar substitutions is presented as well as recent developments relating to organic synthesis. 11.1Scheme 1. Effects of the Cr(CO) 3 entity on the arene ring.Modern Arene Chemistry. Edited by Didier Astruc 368 of negative or positive charges in a side-chain position, (ii) the acidification of the ring protons, which facilitates easy lithiation, and (iii) the large steric effect of the Cr(CO) 3 entity, which blocks one face of the arene and directs incoming reagents to the uncomplexed face of the cycle. The purpose of this chapter is to specifically cover nucleophilic reactions on the activated ring that do not disturb the coordination of the chromium to the arene, namely ipso, cine, and tele nucleophilic aromatic substitutions, and, therefore, open the way to possible double functionalizations that may offer rapid access to interesting synthetic building blocks. 11.1.2 Coverage and DefinitionsReactions in which coordination of the tricarbonylchromium unit to the p-system of an arene cycle 1 activates the ring towards addition of nucleophiles to give h 5 -cyclohexadienyltricarbonylchromium anionic species 2a-d are classified according to the regioselectivity of this addition. If the addition of the nucleophile occurs at the carbon bearing the leaving group, complex 2a can eliminate X À leading to an overall ipso nucleophilic aromatic substitution, S N Ar, affording complex 3a (Scheme 2, path a).If the addition of the nucleophile takes place at another carbon, the intermediates 2b-d can be oxidized to give the free disubstituted arenes 8b-d (Scheme 2, path b). No detailed mechanistic study of this oxidation has been reported in the literature, but it has been Scheme 2. Addition of a nucleophile to arenetricarbonylchromium complexes. 11.1 Introduction 369 Scheme 7. Ipso S N Ar: CaO bond formation. 11.2 Ipso Nucleophilic Aromatic Substitutions 373 Scheme 10. Ipso S N Ar: CaO bond formation. Scheme 11. Ipso S N Ar: CaO bond formation. Scheme 12. Ipso S N Ar: CaO bond formation. 11.2 Ipso Nucleophilic Aromatic Substitutions 375 Scheme 15. Intramolecular ipso S N Ar: CaO bond formation. Scheme 16. Intramolecular ipso S N Ar: CaO bond formation. 11.2 Ipso Nucleophilic Aromatic Substitutions 377 Scheme 27. Ipso S N Ar: CaC bond formation. Scheme 28. Ipso S N Ar: CaC bond formation. 11.2 Ipso Nucleophilic Arom...

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“…The tricarbonylcaromium complexes of be1nfa]anthracene (1), phenanthene (4), 2-acetylphenanthrene (7), and 7, Il-dimethyl benz[a]anthracene (11) were prepared according to the literature" and verified by comparison of tile mp, IH NMR spectra with that of the authentic samples (2,5,9,12).…”

Section: _(116anne)tricarhonylchrqmiummentioning

confidence: 99%

The Regioselective Methylation of Polycyclic Aromatic Hydrocarbons through Tricarbonylchromium Coordination

Own

Chiu

1998

J Chinese Chemical Soc

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Deprotonation, methylation, and air oxidation of polycyclic arenes coordinated to chromium(0), (η6‐arene)Cr(CO)3, produced ring‐methylated products with high selectivity and in good yield. This procedure gave 3‐methylbenz[a]anthracene from (η6‐benz[a]anthracene)Cr(CO)3, 3‐methylphenanthrene from (η6‐phenanthrene)Cr(CO)3, 2‐acetyl‐6‐methylphenanthrene from (η6−2‐acetylphenanthrene)Cr(CO)3, and 3,7,12‐trimethylbenz[a]anthracene from (η6−7,12‐dimethylbenz[a]anthracene)Cr(CO)3.

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Metalation of arenechromium tricarbonyl complexes and electrophilic trapping of the complexed phenyllithium intermediate

Cited by 138 publications

References 1 publication

Regioselective nucleophilic additions to tricarbonyl(η⁶-arene)chromium(0) complexes: electronic versus chelation control

Regioselective nucleophilic additions to tricarbonyl(η⁶-arene)chromium(0) complexes: electronic versus chelation control

Arenetricarbonylchromium Complexes: Ipso , Cine , Tele Nucleophilic Aromatic Substitutions

The Regioselective Methylation of Polycyclic Aromatic Hydrocarbons through Tricarbonylchromium Coordination

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Metalation of arenechromium tricarbonyl complexes and electrophilic trapping of the complexed phenyllithium intermediate

Cited by 138 publications

References 1 publication

Regioselective nucleophilic additions to tricarbonyl(η6-arene)chromium(0) complexes: electronic versus chelation control

Regioselective nucleophilic additions to tricarbonyl(η6-arene)chromium(0) complexes: electronic versus chelation control

Arenetricarbonylchromium Complexes: Ipso , Cine , Tele Nucleophilic Aromatic Substitutions

The Regioselective Methylation of Polycyclic Aromatic Hydrocarbons through Tricarbonylchromium Coordination

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Regioselective nucleophilic additions to tricarbonyl(η⁶-arene)chromium(0) complexes: electronic versus chelation control

Regioselective nucleophilic additions to tricarbonyl(η⁶-arene)chromium(0) complexes: electronic versus chelation control