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. 2020 Oct 14;142(41):17294-17300.
doi: 10.1021/jacs.0c08262. Epub 2020 Sep 30.

C2-Symmetric Dinickel Catalysts for Enantioselective [4 + 1]-Cycloadditions

Michael J Behlen  1 , Christopher Uyeda  1
Affiliations

C2-Symmetric Dinickel Catalysts for Enantioselective [4 + 1]-Cycloadditions

Michael J Behlen et al. J Am Chem Soc. .

Abstract

Dinickel naphthyridine-bis(oxazoline) catalysts promote enantioselective intermolecular [4 + 1]-cycloadditions of vinylidene equivalents and 1,3-dienes. The products of this reaction are methylenecyclopentenes, and the exocyclic alkene is generally obtained with high Z selectivity. E- and Z-dienes react in a stereoconvergent fashion, providing cycloadducts with the same sense of absolute stereochemistry and nearly identical ee values. This feature allows dienes that are commercially available as E/Z mixtures to be used as substrates for the cycloaddition. A DFT model for the origin of asymmetric induction is provided.

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Figures

Figure 1.
Figure 1.
Asymmetric [4 + 1]-cycloaddition reactions of vinylidenes and 1,3-dienes using C2-symmetric dinickel catalysts.
Figure 2.
Figure 2.
(a) Synthesis of (Me2napbox)Ni2(OAc) (2). (b) Comparison of structural parameters for Me2napbox (1) and (Me2napbox)Ni2(OAc) (2) showing bond distances relevant to ligand-based redox activity. (c) Calculated SOMO for (Me2napbox)Ni2(OAc) (2) (BP86/6–311G(d,p) level of DFT). (d) X-band EPR spectra for (Me2napbox)Ni2(OAc) (2) (5.5 K, g = [2.0318, 2.0093]) and (i-PrNDI)Ni2(OAc) (3) (5.5 K, g = [2.0634, 2.0186]). (e) Cyclic voltammograms for (Me2napbox)Ni2(OAc) (2) and (i-PrNDI)Ni2(OAc) (3) (N2 atmosphere, glassy carbon working electrode, 0.3 M [n-Bu4N]PF6 in THF, 100 mV/s scan rate).
Figure 3.
Figure 3.
Substrate Scope Studies. Isolated yields were obtained following purification by column chromatography. Reaction conditions: 1,1-dichloroalkene (0.3 mmol, 1.0 equiv), 1,3-diene (2.0 equiv), catalyst 8 (10 mol%), Zn (3.0 equiv), 5:1 MTBE:DMA (1.0 mL), 35 °C, 48 h. aReactions were run with 15 mol% catalyst loading. bReactions were run with tBunapbox (5 mol%) and Ni(dme)Cl2 (15 mol%).
Figure 4.
Figure 4.
Stereoconvergent cycloadditions with E and Z 1,3-dienes. (a) (E)- and (Z)-1-phenyl-1,3-butadiene undergo [4 + 1]-cycloaddition to provide the same enantiomer of 32. (b) Highly enantioselective cycloadditions with dienes that are commercially available as E/Z mixtures.
Figure 5.
Figure 5.
DFT model for asymmetric induction (BP86/6–311G(d,p) level of DFT): (t-Bunapbox)Ni2Cl, 4, and 1-phenyl-1,3-butadiene. (a) Calculated lowest energy [4 + 1]-cycloaddition pathways leading to the four stereoisomers of cycloadducts 32. Relative free energies for the major pathway are shown in units of kcal/mol. (b) Migratory insertion and reductive elimination transition structures highlighting key steric interactions in pathways leading to minor stereoisomers.
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References

    1. Yoon TP; Jacobsen EN “Privileged chiral catalysts” Science 2003, 299, 1691–1693. - PubMed
    1. Ghosh AK; Mathivanan P; Cappiello J “C2-symmetric chiral bis(oxazoline)–metal complexes in catalytic asymmetric synthesis” Tetrahedron: Asymmetry 1998, 9, 1–45; - PMC - PubMed
    2. Johnson JS; Evans DA “Chiral bis(oxazoline) copper(II) complexes: Versatile catalysts for enantioselective cycloaddition, aldol, michael, and carbonyl ene reactions” Acc. Chem. Res 2000, 33, 325–335; - PubMed
    3. Fache F; Schulz E; Tommasino ML; Lemaire M “Nitrogen-containing ligands for asymmetric homogeneous and heterogeneous catalysis” Chem. Rev 2000, 100, 2159–2232; - PubMed
    4. Desimoni G; Faita G; Quadrelli P “Pyridine-2,6-bis(oxazolines), helpful ligands for asymmetric catalysts” Chem. Rev 2003, 103, 3119–3154; - PubMed
    5. Desimoni G; Faita G; Jørgensen KA “C2-symmetric chiral bis(oxazoline) ligands in asymmetric catalysis” Chem. Rev 2006, 106, 3561–3651; - PubMed
    6. Rasappan R; Laventine D; Reiser O “Metal-bis(oxazoline) complexes: From coordination chemistry to asymmetric catalysis” Coord. Chem. Rev 2008, 252, 702–714;
    7. Babu SA; Krishnan KK; Ujwaldev SM; Anilkumar G “Applications of pybox complexes in asymmetric catalysis” Asian J. Org. Chem 2018, 7, 1033–1053.
    1. Doyle MP “Perspective on dirhodium carboxamidates as catalysts” J. Org. Chem 2006, 71, 9253–9260; - PMC - PubMed
    2. Davies HML; Manning JR “Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion” Nature 2008, 451, 417–424; - PMC - PubMed
    3. Davies HML; Morton D “Guiding principles for site selective and stereoselective intermolecular C-H functionalization by donor/acceptor rhodium carbenes” Chem. Soc. Rev 2011, 40, 1857–1869; - PubMed
    4. Paton RS; Brown JM “Dinuclear palladium complexes—precursors or catalysts?” Angew. Chem., Int. Ed 2012, 51, 10448–10450; - PubMed
    5. Kornecki KP; Berry JF; Powers DC; Ritter T In Prog. Inorg. Chem; Karlin KD, Ed.; John Wiley & Sons, Inc.: Hoboken, New Jersey, 2014; Vol. 58, p 225–302;
    6. Mankad NP “Selectivity effects in bimetallic catalysis” Chem.-Eur. J 2016, 22, 5822–5829; - PubMed
    7. Powers IG; Uyeda C “Metal-metal bonds in catalysis” ACS Catalysis 2017, 7, 936–958;
    8. Farley CM; Uyeda C “Organic reactions enabled by catalytically active metal-metal bonds” Trends in Chem. 2019, 1, 497–509.
    1. Turkenburg LAM; de Worlf WH; Bickelhaupt F “1,4-addition of dichlorocarbene to 1,2-bismethylenecycloheptane” Tetrahedron Lett. 1982, 23, 769–770;
    2. Sugita H; Mizuno K; Mori T; Isagawa K; Otsuji Y “Unusual mode of addition of 1,2-alkadienylidene carbenes to 1,3-dienes: 1,4 addition to rigid and flexible 1,3-dienes” Angew. Chem., Int. Ed 1991, 30, 984–986;
    3. Boisvert L; Beaumier F; Spino C “Evidence for a concerted [4 + 1]- cycloaddition between electron-rich carbenes and electron-deficient dienes” Org. Lett 2007, 9, 5361–5363. - PubMed

    1. Examples of tandem cyclopropanation/1,3-rearrangement reactions:

    2. Danheiser RL; Martinez-Davila C; Auchus RJ; Kadonaga JT. “Stereoselective synthesis of cyclopentene derivatives from 1,3-dienes” J. Am. Chem. Soc 1981, 103, 2443–2446;
    3. Hudlicky T; Koszyk FF; Kutchan TM; Sheth JP “Cyclopentene annulation via intramolecular addition of diazoketones to 1,3-dienes. Applications to the synthesis of cyclopentanoid terpenes” J. Org. Chem 1980, 45, 5020–5027;
    4. Danheiser RL; Bronson JJ; Okano K “Carbanion-accelerated vinylcyclopropane rearrangement. Application in a general, stereocontrolled annulation approach to cyclopentene derivatives” J. Am. Chem. Soc 1985, 107, 4579–4581;
    5. Coscia RW; Lambert TH “Development of a formal [4 + 1] cycloaddition: Pd(OAc)2-catalyzed intramolecular cyclopropanation of 1,3-dienyl β-keto esters and MgI2-promoted vinylcyclopropane−cyclopentene rearrangement” J. Am. Chem. Soc 2009, 131, 2496–2498; - PubMed
    6. Beaumier F; Dupuis M; Spino C; Legault CY “Formal intramolecular (4 + 1)-cycloaddition of dialkoxycarbenes: Control of the stereoselectivity and a mechanistic portrait” J. Am. Chem. Soc 2012, 134, 5938–5953. - PubMed

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