Cobalt(<scp>I</scp>)‐Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkynes and Nitriles: Synthesis of Enantiomerically Enriched Atropoisomers of 2‐Arylpyridines

Gutnov, Andrey; Heller, Bárbara; Fischer, Christine; Drexler, Hans‐Joachim; Spannenberg, Anke; Sundermann, Bernd; Sundermann, Corinna

doi:10.1002/anie.200454164

Cited by 274 publications

(98 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…[7] We have found that a chiral Ir catalyst realizes the new concept for the construction of axial chiralities, and we have already reported a preliminary communication. [8] Quite independently, two groups reported an enantioselective [2 + 2 + 2] cycloaddition based on the same concept: Gutnov and Heller used a chiral Co catalyst under the photoirradiation conditions, [9] and Tanaka used a chiral Rh catalyst. [10] Related papers using enantioselective [2 + 2 + 2] cycloaddition of alkynes were published by the two groups.…”

Section: Introductionmentioning

confidence: 98%

Iridium‐Catalyzed Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes for the Generation of Axial Chiralities

et al. 2006

View full text Add to dashboard Cite

show abstract

Section: Introductionmentioning

confidence: 98%

Iridium‐Catalyzed Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes for the Generation of Axial Chiralities

et al. 2006

View full text Add to dashboard Cite

show abstract

“…The synthesis of chiral 2-arylpyridines was efficiently performed by Gutnov, Heller and co-workers. [14] Chiral pyridines of this type are commonly utilized as ligands in numerous asymmetric transformations. The [2 + 2 + 2] cycloaddition reaction of 2-substituted 1-naphthonitriles with variously substituted alkynes was catalyzed by chiral tartarate-and menthyl-derived cobalt complexes.…”

mentioning

confidence: 99%

[2+2+2] Cycloaddition Reactions Catalyzed by Transition Metal Complexes

2006

View full text Add to dashboard Cite

Recent progress in the synthesis of benzene and 1,3-cyclohexadiene derivatives, and heterocyclic compounds such as pyridines, pyridones, pyrans, pyrimidine diones, etc, has been reviewed. The general mechanistic aspects of the [2 + 2 + 2] cycloaddition reaction are discussed. The asymmetric variants of these reactions are also discussed along with the proposed models of asymmetric induction. Keywords: arenes; catalysis; cycloaddition; heterocycles; metallacycles; transition metals IntroductionThe significance and increasing popularity of [2 + 2 + 2] cycloaddition reactions is evident from the number of reviews that have recently appeared in the literature. [1][2][3] The [2 + 2 + 2] cycloaddition reaction is remarkable in terms of its ability to utilize various unsaturated substrates such as alkynes, diynes, alkenes, imines, isocyanates, isothiocyanates, and CO 2 in the synthesis of a broad variety of highly substituted cyclic molecules such as benzenes, pyridines, pyridones, 1,3-cyclohexadienes, pyrones, thiopyridones and cyclohexanes. Multisubstituted benzenes and pyridines have traditionally been synthesized by aromatic electrophilic substitution (AES) reactions and a variety of metal-mediated coupling reactions. Although, these reactions are extremely efficient, they generally involve multistep syntheses. The application of AES reactions in the synthesis of polysubstituted aromatic rings is limited by the effect of the substituent groups and, hence, it may be very difficult or even impossible to add various functionalities at a specific position on the aromatic ring. On the other hand, [2 + 2 + 2] cycloaddition reactions are extremely atom-efficient and involve the formation of several C À C bonds in a single step. Another important feature of the [2 + 2 + 2] cycloaddition reaction is tolerance of a myriad of functional groups such as alcohols, amines, alkenes, ethers, esters, halogens, and nitriles. Moreover, the availability of numerous catalytic systems that have Adv. Synth. Catal. 2006, 348, 2307 -2327 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 2307 REVIEWS been efficient in tedious syntheses highlights the applicability of the [2 + 2 + 2] cycloaddition reaction. These are important requirements for the [2 + 2 + 2] cycloaddition reaction to become a universal synthetic tool for the synthesis of benzene, pyridine, and other cyclic derivatives. An important problem with the [2 + 2 + 2] cycloaddition reaction is the lack of chemoand regioselectivity observed in earlier reported reactions. However, significant effort has been focused on attaining a high degree of chemo-, regio-and even enantioselectivity with considerable success as evident from recent reports. Excellent reviews on [2 + 2 + 2] cycloaddition reactions are available. Kotha and co-workers have reviewed the synthesis of benzene derivatives by the cyclotrimerization of three alkyne functionalities utilizing transition metal systems as catalysts.[1] Their review is divided into: (a) intermolecular reactionsin which the three pi (alkyn...

show abstract

“…In the authors' opinion, using bulkier substrates (in the presence of catalyst 125, Figure 7.2, Scheme 7.2) led to improved enantioselectivity, with 74-88% ee and > 98% ee after recrystallization [210]. As expected, ees increased from 82 to 93% when lowering the temperature from 20 to -20°C (R = Ph).…”

Section: Co Catalystsmentioning

confidence: 65%

“…In 2004, they took advantage of these results to develop the first asymmetric version of [210]. Moderate yields (traces to 81%) and ees (19-71%) were obtained, and they observed that the enantioselectivity is solvent independent (THF, hexane, dioxane or toluene).…”

Section: Co Catalystsmentioning

confidence: 93%

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

Loxq

Manoury

Poli

et al. 2016

Coordination Chemistry Reviews

295

View full text Add to dashboard Cite

Please cite this article as: P. Loxq, E. Manoury, R. Poli, E. Deydier, A. Labande, Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals, Coordination Chemistry Reviews (2015), http://dx. AbstractAxially chiral biaryl structures are unique systems encountered in various synthetic compounds such as BINAP and BINOL, polymers, but also in natural products presenting a pharmaceutical interest such as Vancomycin, Steganacin or Korupensamine. The axial chirality of these products, so-called atropisomerism, is induced by the restricted rotation around the aryl-aryl bond. This review will summarize the different strategies imagined by chemists to control such chirality, focusing on asymmetric catalytic processes with transition metals. Only transition metal complexes bearing chiral ligands will be considered and the core of this review will consist of the enantioselective coupling of two achiral substrates. Highlights 1. A review on the synthesis of axially chiral biaryls by asymmetric catalysis 2. Exhaustive description of chiral ligands used in the palladium-catalyzed SuzukiMiyaura cross-coupling reaction 3. Emerging reactions such as asymmetric direct C-H functionalization are presented 4. Asymmetric [2+2+2] cycloadditions catalyzed by group 9 transition metals are included

show abstract

Cobalt(I)‐Catalyzed Asymmetric [2+2+2] Cycloaddition of Alkynes and Nitriles: Synthesis of Enantiomerically Enriched Atropoisomers of 2‐Arylpyridines

Cited by 274 publications

References 31 publications

Iridium‐Catalyzed Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes for the Generation of Axial Chiralities

Iridium‐Catalyzed Enantioselective [2+2+2] Cycloaddition of Diynes and Monoalkynes for the Generation of Axial Chiralities

[2+2+2] Cycloaddition Reactions Catalyzed by Transition Metal Complexes

Synthesis of axially chiral biaryl compounds by asymmetric catalytic reactions with transition metals

Contact Info

Product

Resources

About