Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2019 Dec 6;9(12):10887-10893.
Epub 2019 Oct 29.

Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles

Roshan K Dhungana  1 , Shekhar Kc  2 , Prakash Basnet  2 , Vivek Aryal  1 , Lucas J Chesley  1 , Ramesh Giri  1   2
Affiliations

Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles

Roshan K Dhungana et al. ACS Catal. .

Abstract

We disclose a transmetalation-initiated Ni(I)-catalyzed regioselective β,δ-vinylarylation of γ,δ-alkenyl α-cyanocarboxylic esters with vinyl triflates and arylzinc reagents. This reaction proceeds via contraction of six-membered nickellacycles to five-membered nickellacycles to form carbon-carbon bonds at the nonclassical homovicinal sites, and it provides expeditious access to a wide range of complex aliphatic α-cyanoesters, α-cyanocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoamides, monocarboxylic acids, nitriles, and spirolactones. Control, deuterium labeling, and crossover experiments indicate that (i) the nickellacycle contraction occurs by β-H elimination, followed by hydronickellation on transiently formed alkenes, and (ii) the Ni species are stabilized as Ni-enolates.

Keywords: metallacycle contraction; nickel enolates; nickel(I)-catalyzed; regioselective; transmetalation; β,δ-vinylarylation.

PubMed Disclaimer

Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1.
Scheme 1.
Classical Alkene Difunctionalization at Vicinal and Geminal Sites
Scheme 2.
Scheme 2.
Nonclassical Alkene Difunctionalization at Homovicinal Sites by Metallacycle Contraction Process: (A) Previous Work and (B) This Work
Scheme 3.
Scheme 3.
Analysis of Substrate Backbones for Reactivity
Scheme 4.
Scheme 4.
Selective Hydrolysisa aIsolated from 0.3 mmol; dr was determined by 1H NMR of a crude reaction mixture.
Scheme 5.
Scheme 5.
Proposed Catalytic Cycle
Scheme 6.
Scheme 6.
Requirement for an α-Proton
Scheme 7.
Scheme 7.
Deuterium Labeling Experiment
Scheme 8.
Scheme 8.
Crossover Experiment
See this image and copyright information in PMC

References

    1. For reviews, see:

    2. Giri R; Kc S Strategies toward Dicarbofunctionalization of Unactivated Olefins by Combined Heck Carbometalation and Cross-Coupling. J. Org. Chem 2018, 83, 3013–3022. - PubMed
    3. Dhungana RK; Kc S; Basnet P; Giri R Transition Metal-Catalyzed Dicarbofunctionalization of Unactivated Olefins. Chem. Rec 2018, 18, 1314–1340. - PubMed
    4. Derosa J; Tran V; van der Puyl VA; Engle KM Carbon—Carbon π-Bonds as Conjunctive Reagents in Cross-Coupling. Aldrichimica Acta 2018, 51, 21–32.

    1. For dicarbofunctionalization of activated alkenes, see:

    2. Qin T; Cornella J; Li C; Malins LR; Edwards JT; Kawamura S; Maxwell BD; Eastgate MD; Baran PS A General Alkyl-Alkyl Cross-Coupling Enabled by Redox-Active Esters and Alkylzinc Reagents. Science 2016, 352, 801–805. - PMC - PubMed
    3. Guo H-C; Ma J-A Catalytic Asymmetric Tandem Transformations Triggered by Conjugate Additions. Angew. Chem. Int. Ed 2006, 45, 354–366. - PubMed
    4. Zhang L; Lovinger GJ; Edelstein EK; Szymaniak AA; Chierchia MP; Morken JP Catalytic Conjunctive Cross-Coupling Enabled by Metal-Induced Metallate Rearrangement. Science 2016, 351, 70–74. - PMC - PubMed

    1. For alkene dicarbofunctionalization via carbometalation, see:

    2. Nakamura M; Hirai A; Nakamura E Iron-Catalyzed Olefin Carbometalation. J. Am. Chem. Soc 2000, 122, 978–979.
    1. García-Domínguez A; Li Z; Nevado C Nickel-Catalyzed Reductive Dicarbofunctionalization of Alkenes. J. Am. Chem. Soc 2017, 139, 6835–6838. - PubMed
    2. Terao J; Saito K; Nii S; Kambe N; Sonoda N Regioselective Double Alkylation of Styrenes with Alkyl Halides Using a Titanocene Catalyst. J. Am. Chem. Soc 1998, 120, 11822–11823.
    3. Liao L; Jana R; Urkalan KB; Sigman MS A Palladium-Catalyzed Three-Component Cross-Coupling of Conjugated Dienes or Terminal Alkenes with Vinyl Triflates and Boronic Acids. J. Am. Chem. Soc 2011, 133, 5784–5787. - PMC - PubMed
    4. Wu X; Lin H-C; Li M-L; Li L-L; Han Z-Y; Gong L-Z Enantioselective 1,2-Difunctionalization of Dienes Enabled by Chiral Palladium Complex-Catalyzed Cascade Arylation/Allylic Alkylation Reaction. J. Am. Chem. Soc 2015, 137, 13476–13479. - PubMed
    5. Terao J; Nii S; Chowdhury FA; Nakamura A; Kambe N Nickel-Catalyzed Regioselective Three Component Coupling Reaction of Alkyl Halides, Butadienes, and ArM (M = MgX, ZnX). Adv. Synth. Catal 2004, 346, 905–908.
    6. Mizutani K; Shinokubo H; Oshima K Cobalt-Catalyzed Three-Component Coupling Reaction of Alkyl Halides, 1,3-Dienes, and Trimethylsilylmethylmagnesium Chloride. Org. Lett 2003, 5, 3959–3961. - PubMed
    7. Urkalan KB; Sigman MS Palladium-Catalyzed Oxidative Intermolecular Difunctionalization of Terminal Alkenes with Organostannanes and Molecular Oxygen. Angew. Chem., Int. Ed 2009, 48, 3146–3149. - PMC - PubMed
    8. Kuang Z; Yang K; Song Q Pd-Catalyzed Regioselective 1,2-Difunctionalization of Vinylarenes with Alkenyl Triflates and Aryl Boronic Acids at Ambient Temperature. Org. Lett 2017, 19, 2702–2705. - PubMed
    9. Kc S; Dhungana RK; Shrestha B; Thapa S; Khanal N; Basnet P; Lebrun RW; Giri R Ni-Catalyzed Regioselective Alkylarylation of Vinylarenes via C(sp3)–C(sp3)/C(sp3)–C(sp2) Bond Formation and Mechanistic Studies. J. Am. Chem. Soc 2018, 140, 9801–9805. - PubMed
    10. Gao P; Chen L-A; Brown MK Nickel-Catalyzed Stereoselective Diarylation of Alkenylarenes. J. Am. Chem. Soc 2018, 140, 10653–10657. - PMC - PubMed
    11. Anthony D; Lin Q; Baudet J; Diao T Nickel-Catalyzed Asymmetric Reductive Diarylation of Vinylarenes. Angew. Chem., Int. Ed 2019, 58, 3198–3202. - PMC - PubMed
    12. Klauck FJR; Yoon H; James MJ; Lautens M; Glorius F Visible-Light-Mediated Deaminative Three-Component Dicarbofunctionalization of Styrenes with Benzylic Radicals. ACS Catal. 2019, 9, 236–241.
    13. Yong X; Han Y-F; Li Y; Song R-J; Li J-H Alkylarylation of Styrenes via Direct C(sp3)–Br/C(sp2)–H Functionalization Mediated by Photoredox and Copper Cooperative Catalysis. Chem. Commun 2018, 54, 12816–12819. - PubMed
    14. Ouyang X-H; Hu M; Song R-J; Li J-H Oxidative Three-Component 1,2-Alkylarylation of Alkenes with Alkyl Nitriles and N-Heteroarenes. Chem. Commun 2018, 54, 12345–12348. - PubMed
    15. Ouyang X-H; Cheng J; Li J-H 1,2-Diarylation of Alkenes with Aryldiazonium Salts and Arenes Enabled by Visible Light Photoredox Catalysis. Chem. Commun 2018, 54, 8745–8748. - PubMed
    16. Ouyang X-H; Li Y; Song R-J; Hu M; Luo S; Li J-H Intermolecular Dialkylation of Alkenes with Two Distinct C(sp3)-H Bonds Enabled by Synergistic Photoredox Catalysis and Iron Catalysis. Sci. Adv 2019, 5, No. eaav9839. - PMC - PubMed
    1. Saini V; Sigman MS Palladium-Catalyzed 1,1-Difunctionalization of Ethylene. J. Am. Chem. Soc 2012, 134, 11372–11375. - PMC - PubMed
    2. Werner EW; Urkalan KB; Sigman MS PdII-Catalyzed Oxidative 1,1-Diarylation of Terminal Olefins. Org. Lett 2010, 12, 2848–2851. - PMC - PubMed
    3. Saini V; Liao L; Wang Q; Jana R; Sigman MS Pd(0)-Catalyzed 1,1-Diarylation of Ethylene and Allylic Carbonates. Org. Lett 2013, 15, 5008–5011. - PMC - PubMed

LinkOut - more resources