Selective Hydroarylation of 1,3‐Diynes Using a Dimeric Manganese Catalyst: Modular Synthesis of Z‐Enynes

Yan, Zhongfei; Yuan, Xiang‐Ai; Zhao, Yue; Zhu, Chengjian; Xie, Jin

doi:10.1002/ange.201807851

Cited by 20 publications

(5 citation statements)

References 66 publications

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“…The same group described the regio-and stereoselective hydroarylation of 2,4-diyne propargyl alcohols with boronic acids catalyzed by Mn 2 (CO) 8 Br 2 (Scheme 6). 22 Mechanistic studies suggest that the reaction proceeds through acetateinduced dissociation of the dimeric structure Mn 2 (CO) 8 Br 2 to deliver the active Mn I species. Transmetalation with the boronic acid would afford Ar−Mn I species with an open coordination site for alkyne coordination, in which a OHπ interaction between the alcohol and the aryl group was identified by DFT studies.…”

Section: Hydroarylation Of Internal Alkynesmentioning

confidence: 99%

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

et al. 2021

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Catalytic functionalization of alkynes with organoboron reagents provides a straightforward access to stereochemically defined multisubstituted alkenes, which are structural motifs commonly found in bioactive compounds and organic materials. Recent progress has substantially broadened the scope of this field on several fronts. Strategies for regioselectivity control in the 1,2-migratory insertion across unsymmetrical internal alkynes, as well as for the direct access to products with anti-insertion stereochemistry, have been devised. The alkenyl-to-aryl 1,4-metal migration upon metal insertion has been recently exploited in powerful cascade sequences leading to complex polycyclic scaffolds, including the development of enantioselective processes. Elegant enantiospecific and dynamic kinetic resolution methods have been developed for accessing chiral allenes from propargylic alcohol derivatives. Mechanistic manifolds have emerged based on single-electron transfer (SET) that have provided a fresh impetus for alkyne 1,2-difunctionalization with complementary stereoselectivity to processes relying on 1,2-insertion of R–M species. Herein, we discuss the most recent advances in transition-metal-catalyzed functionalization of alkynes using organoboron reagents, categorized according to the type of mechanistic outcome. Emphasis is placed on mechanistic aspects, synthetic utility, limitations, and challenges for future research.

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Section: Hydroarylation Of Internal Alkynesmentioning

confidence: 99%

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

et al. 2021

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“…10 Thereby, strategies for the incorporation of fluorine into organic molecules, and organic reactions involving substrates with fluorine substituents, have become a blossoming field in the last decade. 11 The use of complex building blocks such as enynes, 12 which are organic compounds having a C=C double bond (alkene) and a C≡C triple bond (alkyne), has given access to more sophisticated structures under transition-metal catalysis using Au, 13 14 Ag, 15 Rh, 16 17 Ru, 18 Mn, 19 Pd, 20 and Ir, 21 22 among others.…”

Section: Introductionmentioning

confidence: 99%

A Density Functional Theory Study on the Cobalt-Mediated Intramolecular Pauson–Khand Reaction of Enynes Containing a Vinyl Fluoride Moiety

Escorihuela¹

2022

Synthesis

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The Co2(CO)8-mediated intramolecular Pauson–Khand reaction (PKR) is an effective method for constructing polycyclic structures. Recently, our group reported a series of this type of reaction involving fluorinated enynes that proceed with reasonable reaction rates and yields. However, mechanistic studies involving these fluorinated derivatives in intramolecular PKR are scarce. In this study, density functional theory calculations are used to clarify the mechanism and reactivity of enynes containing a vinyl fluoride moiety for this reaction. In agreement with previous studies, alkene insertion is considered to be the rate-determining step for the overall Pauson–Khand reaction of enynes containing a vinyl fluoride moiety. The effect of the substituent on the Co2(CO)8-mediated intramolecular Pauson–Khand reaction has also been investigated. When introducing heteroatoms as tethering units, the fluorinated enynes exhibited lower reactivity than the malonate homologues, whereas the use of a sulfur-based tether was unsuccessful. This computational study provides detailed information about the PKR mechanism and transition-state structures, and the results are validated with previous experimental results.

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“…Various routes to architecturally analogous 1,3-enynes that contain a trisubstituted alkene moiety [43][44][45][46][47][48][49][50][51][52][53][54] have been developed, but the majority focused on two-component systems involving coupling reactions of elaborated alkynes/alkenes as starting materials. 43,[47][48][51][52][53][54] Threecomponent catalytic regimes [44][45][46]49 starting from simpler, more readily accessible substrates offer a more practical approach to expeditiously assemble the desired products. However, these methods suffer from a number of shortcomings.…”

mentioning

confidence: 99%

Nickel-Catalyzed Site- and Stereoselective Reductive Alkylalkynylation of Alkynes

Jiang¹,

Pan²,

Yang³

et al. 2020

Preprint

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Development of a catalytic multicomponent reaction by orthogonal activation of readily available substrates for the streamlined difunctionalization of alkynes is a compelling objective in organic chemistry. Alkyne carboalkynylation, in particular, offers a direct entry to valuable 1,3-enynes with different substitution patterns. Here, we show that the synthesis of stereodefined 1,3-enynes featuring a trisubstituted olefin is achieved by merging alkynes, alkynyl bromides and redox-active N-(acyloxy)phthalimides through nickel-catalyzed reductive alkylalkynylation. Products are generated in up to 89% yield as single regio- and E isomers. Transformations are tolerant of diverse functional groups and the resulting 1,3-enynes are amenable to further elaboration to synthetically useful building blocks. With olefin-tethered N-(acyloxy)phthalimides, a cascade radical addition/cyclization/alkynylation process can be implemented to obtain 1,5-enynes. The present study underscores the crucial role of redox-active esters as superior alkyl group donors compared to haloalkanes in reductive alkyne dicarbofunctionalizations.

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Selective Hydroarylation of 1,3‐Diynes Using a Dimeric Manganese Catalyst: Modular Synthesis of Z‐Enynes

Cited by 20 publications

References 66 publications

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

Transition-Metal-Catalyzed Functionalization of Alkynes with Organoboron Reagents: New Trends, Mechanistic Insights, and Applications

A Density Functional Theory Study on the Cobalt-Mediated Intramolecular Pauson–Khand Reaction of Enynes Containing a Vinyl Fluoride Moiety

Nickel-Catalyzed Site- and Stereoselective Reductive Alkylalkynylation of Alkynes

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