Iridium Complex-Catalyzed Highly Enantio- and Diastereoselective [2+2+2] Cycloaddition for the Synthesis of Axially Chiral Teraryl Compounds

Shibata, Takanori; Fujimoto, Takayoshi; Yokota, Kazuhisa; Takagi, Kentaro

doi:10.1021/ja048131d

Cited by 210 publications

(50 citation statements)

References 25 publications

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“…In our preceding communication, [8] the [2 + 2 + 2] cycloaddition of a,w-diynes and monoalkynes was examined at 100 8C using Ir-MeDUPHOS catalyst, which was prepared in situ from [IrClA C H T U N G T R E N N U N G (cod)] 2 and (S,S)-MeDUPHOS. In the case of the reaction of the oxygen-tethered diyne 1a with 1,4-dimethoxybut-2-yne (2a), diyne 1a was consumed promptly and only a dl isomer of the teraryl compound 3aa was obtained in almost perfect enantioselectivity (Table 1, Entry 1) and (R,R)-MeDUPHOS surely induced the opposite enantiomer (Entry 2).…”

Section: Resultsmentioning

confidence: 99%

“…In our preceding communication, [8] symmetrical and protected diols, such as 1,4-dimethoxybut-2-yne (2a), were used as coupling partners for diynes. We further examined but-2-yne-1,4-diol (2b), a symmetrical but non-protected diol using the same chiral catalyst {henceforth, the catalyst, which was prepared in situ from [IrClA C H T U N G T R E N N U N G (cod)] 2 and (S,S)-MeDUPHOS, is described as "chiral Ir catalyst"} ( Table 2).…”

Section: Diol or Monool As A Coupling Partnermentioning

confidence: 99%

“…[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: 99%

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

et al. 2006

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Section: Resultsmentioning

confidence: 99%

Section: Diol or Monool As A Coupling Partnermentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2006

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“…Shibata and co-workers have utilized the [2 + 2 + 2] cycloaddition of an a,w-diyne (possessing an orthosubstituted aryl on its terminus) and a disubstituted alkyne in the synthesis of axially chiral aryl compounds. [21] They postulated the formation of an axially chiral teraryl compound due to the restricted rotation across the central C À C bond as a result of steric hindrance between the ortho-substituents on the diyne aryl functionality and the substituents on the newly formed benzene ring. As expected, the use of a chiral ligand in this reaction afforded axially chiral diols in high enantiomeric excess (Scheme 13).…”

Section: Synthesis Of Substituted Benzene Derivativesmentioning

confidence: 99%

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

2006

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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...

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“…Um exemplo recente desta abordagem foi a cicloadição [2+2+2] de α,ω-diinos e monalquinos catalisada por um complexo de irídio, a qual permitiu a síntese de compostos axialmente quirais 24 (Esquema 18).…”

Section: Reações De Cicloadiçãounclassified

Síntese de indanos: uma seleção de métodos gerais e eficientes

Ferraz¹,

Aguilar²,

Silva³

et al. 2005

Quím. Nova

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Recebido em 16/8/04; aceito em 1/10/04; publicado na web em 17/2/05 SYNTHESIS OF INDANS: A SELECTION OF GENERAL AND EFFICIENT METHODS. The indan ring system is present in several compounds with important pharmacological properties. In this account recent examples of selected methods (Friedel-Crafts acylation, cycloaddition reactions, ring contraction, cyclization and resolution) for the synthesis of indans are discussed.

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Iridium Complex-Catalyzed Highly Enantio- and Diastereoselective [2+2+2] Cycloaddition for the Synthesis of Axially Chiral Teraryl Compounds

Cited by 210 publications

References 25 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

Síntese de indanos: uma seleção de métodos gerais e eficientes

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