Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution

Suzuki, Shunsuke; Shibata, Yu; Tanaka, Ken

doi:10.1002/chem.202000010

Cited by 6 publications

(2 citation statements)

References 53 publications

(19 reference statements)

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“…In addition, the synthetic practicability of the reaction has been confirmed in the further application In 2020, the Tanaka group reported an enantioselective [2 + 2 + 2] cycloaddition of 1,6-enynes with allylic alcohols, which enabled preparation of optically active bicyclic cyclohexenes bearing three stereogenic centers with excellent enantioselectivity (Scheme 86). [67] This Rh-catalyzed protocol employing cationic rhodium(I) complex as the catalyst, P-phos as the ligand, afforded the valuable chiral bicyclic cyclohexenes with broad substrate scope. Some experiments were performed by authors to investigate the tentative mechanism, which revealed that the reaction proceeded via the kinetic resolution of the racemic secondary allylic alcohols.…”

Section: Rh-catalyzed Reaction Of 16-enynesmentioning

confidence: 99%

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Liu,

Xu,

Han

et al. 2024

Adv Synth Catal

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Elaborated molecular architectures, specifically those bearing one or more carbon stereocenters, stand as an important class of carbocyclic and heterocyclic frameworks because they are frequently occurring core structures in numerous natural products and biologically active pharmaceutical molecules. Over the past few decades, the development of novel and versatile synthetic approaches via cascade cyclization reactions of 1,6‐enynes for the construction of a series of fused and spiro compounds has been the focus of a great deal of research initiatives. These synthesis strategies are peculiarly fascinating in the context of the assembly of a wide array of pharmaceutical molecules, natural products, agrochemicals, and functional materials. In this review, recent developments in the transformations of 1,6‐enynes with diverse coupling reagents are summarized since 2018, which could be divided into five categories: 1) Introduction; 2) Transition metal catalyzed cyclization of 1,6‐enynes; 3) Metal‐free cyclization of 1,6‐enynes; 4) Visible‐light‐induced cyclization of 1,6‐enynes; 5) Electrocatalytic cyclization of 1,6‐enynes.

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Section: Rh-catalyzed Reaction Of 16-enynesmentioning

confidence: 99%

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Liu,

Xu,

Han

et al. 2024

Adv Synth Catal

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“…The reaction of various enynes with 5 equiv of a racemic secondary allylic alcohol proceeded at room temperature in the presence of [Rh(cod) 2 ]BF 4 as the rhodium source and (R)-P-Phos as a ligand to afford, through a kinetic resolution of the alcohol, the corresponding bicyclic cyclohexenes bearing three stereocenters, as single diastereomers in 20-79% yield and 90->99% ee (Scheme 37). 99 Various alkyl or aryl substituents were tolerated on the enyne partner whereas for the allylic alcohol, 1-phenylprop-2-en-1-ol derivatives having electronically and sterically diverse substituents on the benzene ring were suitable.…”

Section: Scheme 36mentioning

confidence: 99%

Recent Progress in Metal-Catalyzed [2+2+2] Cycloaddition Reactions

Matton¹,

Huvelle²,

Haddad³

et al. 2021

Synthesis

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Metal-catalyzed [2+2+2] cycloaddition is a powerful tool that allows rapid construction of functionalized 6-membered carbo- and heterocycles in a single step through an atom-economical process with high functional group tolerance. The reaction is usually regio- and chemoselective although selectivity issues can still be challenging for intermolecular reactions involving the cross-[2+2+2] cycloaddition of two or three different alkynes and various strategies have been developed to attain high selectivities. Furthermore, enantioselective [2+2+2] cycloaddition is an efficient means to create central, axial, and planar chirality and a variety of chiral organometallic complexes can be used for asymmetric transition-metal-catalyzed inter- and intramolecular reactions. This review summarizes the recent advances in the field of [2+2+2] cycloaddition.1 Introduction2 Formation of Carbocycles2.1 Intermolecular Reactions2.1.1 Cyclotrimerization of Alkynes2.1.2 [2+2+2] Cycloaddition of Two Different Alkynes2.1.3 [2+2+2] Cycloaddition of Alkynes/Alkenes with Alkenes/Enamides2.2 Partially Intramolecular [2+2+2] Cycloaddition Reactions2.2.1 Rhodium-Catalyzed [2+2+2] Cycloaddition2.2.2 Molybdenum-Catalyzed [2+2+2] Cycloaddition2.2.3 Cobalt-Catalyzed [2+2+2] Cycloaddition2.2.4 Ruthenium-Catalyzed [2+2+2] Cycloaddition2.2.5 Other Metal-Catalyzed [2+2+2] Cycloaddition2.3 Totally Intramolecular [2+2+2] Cycloaddition Reactions3 Formation of Heterocycles3.1 Cycloaddition of Alkynes with Nitriles3.2 Cycloaddition of 1,6-Diynes with Cyanamides3.3 Cycloaddition of 1,6-Diynes with Selenocyanates3.4 Cycloaddition of Imines with Allenes or Alkenes3.5 Cycloaddition of (Thio)Cyanates and Isocyanates3.6 Cycloaddition of 1,3,5-Triazines with Allenes3.7 Cycloaddition of Aldehydes with Enynes or Allenes/Alkenes3.8 Totally Intramolecular [2+2+2] Cycloaddition Reactions4 Conclusion

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Enantioselective Construction of 5‐6‐5 Tricyclic Lactone Framework Bearing a Quaternary Bridgehead Carbon via Rh‐Catalyzed Asymmetric [2+2+2] Cycloaddition of Enediynes

et al. 2021

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Herein, we report a Rh-catalyzed asymmetric [2 + 2 + 2] cycloaddition of ene-yne-yne enediynes to generate enantio-enriched tricyclic cyclohexadienes bearing a quaternary bridgehead carbon. We found that the Rh-Phanephos complex is an appropriate catalyst for the cycloaddition of enediynes bearing an unsubstituted propiolate terminus, whereas Rh-biaryl bisphosphine catalysts, which have been widely used for asymmetric cycloadditions of alkynes and alkenes, are not applicable for the reaction of such enediynes. Several control experiments suggest that the reaction using the Rh-Phanephos complex exclusively proceeds via a rhodacyclopentadiene intermediate, unlike when using a Rh-biaryl bisphosphine complex that can form a rhodacyclopentadiene intermediate as well as a rhodacyclopentene intermediate in a substratedependent manner.

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Rhodium‐Catalyzed Asymmetric [2+2+2] Cycloaddition of 1,6‐Enynes with Racemic Secondary Allylic Alcohols through Kinetic Resolution

Cited by 6 publications

References 53 publications

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Recent Advances in Cyclization Reactions of 1,6‐Enynes

Recent Progress in Metal-Catalyzed [2+2+2] Cycloaddition Reactions

Enantioselective Construction of 5‐6‐5 Tricyclic Lactone Framework Bearing a Quaternary Bridgehead Carbon via Rh‐Catalyzed Asymmetric [2+2+2] Cycloaddition of Enediynes

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