A New Route to Substituted Phenols by Cationic Rhodium(I)/BINAP Complex-Catalyzed Decarboxylative [2 + 2 + 2] Cycloaddition

Hara, Hiromi; Hirano, Masao; Tanaka, Ken

doi:10.1021/ol900123d

Cited by 76 publications

(34 citation statements)

References 36 publications

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“…New routes for the rapid preparation of substituted phenols and anilines based on a partially intermolecular [2 + 2 + 2] cycloaddition reaction of 1,6‐ and 1,7‐diynes as key‐step have been explored respectively by Tanaka's [51] and Louie's [52] groups under rhodium catalysis. According to their strategies, unstable hydroxyacetylene and free ynamine can be easily replaced by equivalent forms consisting in vinylene carbonate and 2‐oxazolone.…”

Section: [2+2+2] Cycloaddition Reactionsmentioning

confidence: 99%

Alkyne Surrogates in Cycloaddition Reactions for the Preparation of Molecules of Interest

2021

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Although alkynes are very good partners for cycloaddition reactions, their use is often associated to several drawbacks, such as multi‐steps synthesis, selectivity and stability issues or difficulty to handle for alkynes with low boiling point. In this context, alkyne surrogates have emerged as alternative substitution partners unlocking new opportunities. This review intends to highlight the outstanding power and utility of such compounds for the preparation of high value molecules.

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Section: [2+2+2] Cycloaddition Reactionsmentioning

confidence: 99%

Alkyne Surrogates in Cycloaddition Reactions for the Preparation of Molecules of Interest

2021

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“…In this way, benzene rings were prepared avoiding selectivity problems. Several groups have reported the use of enol ethers, vinylene carbonates, or 2‐oxazolones as an alkyne equivalents that undergo dehydration after the cyclotrimerization giving the aromatic final product. If the enol ether component is replaced by vinylene carbonate, a phenol is obtained, whereas the reaction with 2‐oxazolones gives anilines.…”

Section: Rhodium and Iridium Catalysismentioning

confidence: 99%

Alkenes in [2+2+2] Cycloadditions

Domı́nguez

Pérez‐Castells

2016

Chemistry A European J

127

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Participation of alkenes and allenes in [2+2+2] cycloaddition reactions has attracted much attention recently. This version of the well-established alkyne cyclotrimerization renders interesting products, such as cyclohexadienes and other polycycles, through cascade processes. Many mechanistic variations are observed when using certain metal complexes as catalysts. The frequent generation of stereogenic centers has prompted the development of efficient asymmetric versions. This Minireview summarizes the efforts reported to date on the use of double bonds as partners in [2+2+2] cyclotrimerizations.

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“…Tanaka and co-workers also reported a similar methodology utilizing a different leaving group. 42 Zhang and Louie extended this approach to the synthesis of anilines 71 using 2-oxazolone (70), which can be used as an alternative for ynamides (Scheme 27). 43 They also demonstrated that the reaction proceeds with full regioselectivity when two different R groups are used (e.g., H, Me).…”

Section: Other [2+2+2] Approachesmentioning

confidence: 99%

Recent Advances in Transition-Metal-Catalyzed [2+2+2]-Cyclo(co)trimerization Reactions

Broere¹,

Ruijter²

2012

Synthesis

195

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Transition-metal-catalyzed [2+2+2] cyclo(co)trimerization reactions are a powerful methodology to synthesize various complex multi-substituted (poly)cyclic molecules in a single step with optimal atom efficiency. Ever since the discovery, the reaction has been plagued by issues concerning regio-and chemoselectivity. Over the last decades many advances have been made to overcome these issues by, for example, employing regio-directing groups or tethering the reaction partners together in an intramolecular approach. These solutions, however, have certain limitations. Nowadays, it is also possible to synthesize chiral molecules by performing an asymmetric transition-metal-catalyzed [2+2+2]-cyclo(co)trimerization reaction. This review focuses on the recent advances in mechanistic insight, solving the regioselectivity issue, synthesis of chiral molecules and alternative approaches for the synthesis of substituted benzenes, pyridines and 2-pyridones. In addition, recent applications in areas such as total synthesis of natural products are also described, demonstrating that the transition-metalcatalyzed [2+2+2]-cyclo(co)trimerization reaction is a powerful tool and a welcome addition to the chemist's 'synthetic toolbox'.

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A New Route to Substituted Phenols by Cationic Rhodium(I)/BINAP Complex-Catalyzed Decarboxylative [2 + 2 + 2] Cycloaddition

Abstract: A new route to substituted phenols has been developed by cationic rhodium(I)/BINAP complex-catalyzed decarboxylative [2 + 2 + 2] cycloadditions of 1,6- and 1,7-diynes with commercially available vinylene carbonate.

Cited by 76 publications

References 36 publications

Alkyne Surrogates in Cycloaddition Reactions for the Preparation of Molecules of Interest

Alkyne Surrogates in Cycloaddition Reactions for the Preparation of Molecules of Interest

Alkenes in [2+2+2] Cycloadditions

Recent Advances in Transition-Metal-Catalyzed [2+2+2]-Cyclo(co)trimerization Reactions

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