Transition-Metal-Mediated Dearomatization Reactions

Pape, Andrew R.; Kaliappan, Krishnapillat; Kündig, E. Peter

doi:10.1021/cr9902852

Cited by 721 publications

(280 citation statements)

References 145 publications

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“…A long review, titled "Transition-MetalMediated Dearomatization Reactions" 2 , that appeared two years later only briefly mentioned cine-and telesubstitutions in arenetricarbonylchromium complexes, noting that both reactions probably involved the following sequence of reactions: nucleophilic addition, protonation, isomerization and elimination to reconstruct aromatic system (4 references). In 2001, we published the first general review article 3 on the cineand tele-substitutions describing these types of reactions in homoarenes, heteroarenes and aliphatic systems, regardless of nucleophilic, electrophilic or radical mechanisms of the reactions (210 references).…”

Section: Introductionmentioning

confidence: 99%

cine- and tele-Substitution reactions: review of work from 2002-2016

Suwiński¹

2017

Arkivoc

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This report brings new facts and achievements on the cine-and tele-substitutions reactions published in the last fifteen years. The reactions occurred primarily in such systems as nitroarenes, metal homoarene complexes, and five-or six-membered heteroarenes. Sometimes similar reactions were also observed in other systems, including non-aromatic. cine-and tele-Substitution reactions are presented here independently of their mechanisms.

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Section: Introductionmentioning

confidence: 99%

cine- and tele-Substitution reactions: review of work from 2002-2016

Suwiński¹

2017

Arkivoc

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“…6,7 Well-studied examples of dearomatization processes include Birch reduction, [8][9][10][11] enzymatic cis-dihydroxylation, [12][13][14] oxidative dearomatization of phenols, [15][16][17][18][19][20][21] enzymatic benzene reductions, 22 transition-metal complexing dearomatizations, [23][24][25] nucleophilic dearomatization processes [26][27][28][29][30][31] and catalytic hydrogenation. [32][33][34][35] An alternative dearomatization process would involve a [4+2] or [3+2] cycloaddition reaction of a diene or 1,3-dipole with an aromatic carbon-carbon double bond.…”

Section: Introductionmentioning

confidence: 99%

1,3-Dipolar cycloaddition reactions of azomethine ylides with aromatic dipolarophiles

Ryan

2015

Arkivoc

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The 1,3-dipolar cycloadditions of azomethine ylides to aromatic dipolarophiles are reviewed and discussed. The reaction proceeds with stabilized and non-stabilized azomethine ylides, although most studies have been with non-stabilized systems. While simple benzene derivatives do not readily undergo such 1,3-dipolar cycloaddition reactions, the dipolarophilic character of benzene emerges when the benzenoid nucleus is embedded within a polycyclic aromatic hydrocarbon, tethered with the azomethine ylide (an intramolecular process) or substituted with highly electron withdrawing nitro groups. Heteroaromatic systems display similar tendencies towards such cycloaddition processes. The review closes with a consideration of the mechanism of the reactions.

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“…Arene dearomatization reactions can also be induced by temporary complexation of its π-system to a transition metal with the fragments Cr(CO) 3 , Mn(CO) 3 + , and Os(NH 3 ) 5 2+ being most prominent [14]. Recently, this has been extended to the CpRu + - [15,16] and Mo(CO) 3 -fragments [17].…”

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confidence: 99%

“…Tricarbonylchromium-mediated dearomatization provides an efficient direct access to substituted cyclohexadienes [14]. Up to three C-substituents can be added in a regioselective and stereoselective manner across an arene double bond in a one-pot sequence (Scheme 1).…”

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confidence: 99%

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Stereoselective chromium- and molybdenum-mediated transformations of arenes

Kündig

Cannas

Fabritius

et al. 2004

Pure and Applied Chemistry

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Tricarbonylchromium-mediated dearomatization provides a rapid access to substituted cyclohexadienes. Efficient asymmetric routes to planar chiral arene complexes and to substituted cyclohexadienes have been developed. The article sums up the main features of this chemistry. Highly enantiomerically enriched ortho-substituted benzaldehyde complexes are accessible via asymmetric lithiation followed by trapping with electrophiles. In different solvents, the trimethylsilyl complex exhibits [α] values ranging from -174 to +108 for the same enantiomer. Details of two asymmetric syntheses of natural products are given: the alkaloid lasubine I starting from a highly enantiomerically enriched planar chiral arene complex and the marine furanosesquiterpene acetoxytubipofuran. The latter is assembled via asymmetric dearomatization of a benzaldehyde imine complex. Other key steps include an Eschenmoser-Claisen rearrangement and a regio-and diastereoselective Pd-catalyzed allylic substitution. The final section deals with labile arene metal complexes. For the first time, dearomatization reactions mediated by the Mo(CO) 3 group have been realized. The reactions show strong analogies to the Cr(CO) 3 -mediated reactions, but exhibit also marked differences: the arene-Mo bond is stronger, but more labile, and the sequential double additions show different selectivities compared to the chromium analogs.The search for ever more efficient chemo-, regio-, and stereoselective routes to complex molecules from simple starting materials is an important task in organic synthesis. Progress in this area continues to advance at a fast pace. Arenes, the subject of this article, are widely available, highly stable, and readily derivatized through reactions such as electrophilic and nucleophilic aromatic substitution [1], ortholithiation followed by reaction with electrophiles [2], or metal-catalyzed substitution and coupling reactions [3][4]. Routes to differentially substituted aromatic products are thus well established. Benzene and its derivatives are attractive starting materials because they have the potential to provide a rapid entry into complex alicyclic synthetic building blocks containing unmasked functionality, new carbon-carbon bonds, and new stereogenic centers [5]. However, this route to functionalized nonaromatic six-membered carbocycles is not common because substitutive dearomatization reactions require disruption of the aromatic π-system and this severely limits the scope of viable methodologies.This notwithstanding, the synthesis of complex organic molecules via elegant dearomatization chemistry has undergone intensive investigation. Examples involve the Birch reduction, which achieves *Plenary and invited lectures presented at the

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Transition-Metal-Mediated Dearomatization Reactions

Cited by 721 publications

References 145 publications

cine- and tele-Substitution reactions: review of work from 2002-2016

cine- and tele-Substitution reactions: review of work from 2002-2016

1,3-Dipolar cycloaddition reactions of azomethine ylides with aromatic dipolarophiles

Stereoselective chromium- and molybdenum-mediated transformations of arenes

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