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Boron-mediated modular assembly of tetrasubstituted alkenes

  • Flynn, A. B. & Ogilvie, W. W. Stereocontrolled synthesis of tetrasubstituted olefins. Chem. Rev. 107, 4698–4745 (2007).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Negishi, E.-i et al. Recent advances in efficient and selective synthesis of di-, tri-, and tetrasubstituted alkenes via Pd-catalyzed alkenylation–carbonyl olefination synergy. Acc. Chem. Res. 41, 1474–1485 (2008).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Buttard, F., Sharma, J. & Champagne, P. A. Recent advances in the stereoselective synthesis of acyclic all-carbon tetrasubstituted alkenes. Chem. Commun. 57, 4071–4088 (2021).

    Article 
    CAS 

    Google Scholar
     

  • Paek, S.-M. Synthesis of tetrasubstituted alkenes via metathesis. Molecules 17, 3348–3358 (2012).

    Article 
    CAS 
    PubMed 
    PubMed Central 

    Google Scholar
     

  • Mukherjee, N., Planer, S. & Grela, K. Formation of tetrasubstituted C–C double bonds via olefin metathesis: challenges, catalysts, and applications in natural product synthesis. Org. Chem. Front. 5, 494–516 (2018).

    Article 
    CAS 

    Google Scholar
     

  • Soderquist, J. A. & Najafi, M. R. Selective oxidation of organoboranes with anhydrous trimethylamine N-oxide. J. Org. Chem. 51, 1330–1336 (1986).

    Article 
    CAS 

    Google Scholar
     

  • Armstrong, R. J. & Aggarwal, V. K. 50 years of Zweifel olefination: a transition-metal-free coupling. Synthesis 49, 3323–3336 (2017).

    Article 
    CAS 
    PubMed Central 

    Google Scholar
     

  • Zweifel, G., Arzoumanian, H. & Whitney, C. C. A convenient stereoselective synthesis of substituted alkenes via hydroboration-iodination of alkynes. J. Am. Soc. Chem. 89, 3652–3653 (1967).

    Article 
    CAS 

    Google Scholar
     

  • Normant, J. F. & Alexakis, A. Carbometallation (C-metallation) of alkynes: stereospecific synthesis of alkenyl derivatives. Synthesis 1981, 841–870 (1981).

    Article 

    Google Scholar
     

  • Yoshida, H. Borylation of alkynes under base/coinage metal catalysis: some recent developments. ACS Catal. 6, 1799–1811 (2016).

    Article 
    CAS 

    Google Scholar
     

  • Polák, P., Váňová, H., Dvořák, D. & Tobrman, T. Recent progress in transition metal-catalyzed stereoselective synthesis of acyclic all-carbon tetrasubstituted alkenes. Tetrahedron Lett. 57, 3684–3693 (2016).

    Article 

    Google Scholar
     

  • Thomas, S. P., French, R. M., Jheengut, V. & Aggarwal, V. K. Homologation and alkylation of boronic esters and boranes by 1,2-metallate rearrangement of boron ate complexes. Chem. Rec. 9, 24–39 (2009).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Wang, H., Jing, C., Noble, A. & Aggarwal, V. K. Stereospecific 1,2-migrations of boronate complexes induced by electrophiles. Angew. Chem. Int. Ed. 59, 16859–16872 (2020).

    Article 
    CAS 

    Google Scholar
     

  • Matteson, D. S., Collins, B. S. L., Aggarwal, V. K. & Ciganek, E. in Organic Reactions 427–860 (Wiley, 2021).

  • Corey, E. J. & Cimprich, K. A. Highly enantioselective alkynylation of aldehydes promoted by chiral oxazaborolidines. J. Am. Soc. Chem. 116, 3151–3152 (1994).

    Article 
    CAS 

    Google Scholar
     

  • Chen, H. & Deng, M.-Z. Nickel-catalyzed allylation of lithium 1-alkynyl(trialkoxy)borates with 1,3-disubstituted allyl carbonates. J. Organomet. Chem. 603, 189–193 (2000).

    Article 
    CAS 

    Google Scholar
     

  • Negishi, E.-i Chemistry of organoborates. J. Organomet. Chem. 108, 281–324 (1976).

    Article 
    CAS 

    Google Scholar
     

  • Pelter, A., Smith, K. in Comprehensive Organic Chemistry Vol. 3 (eds Barton, D., Ollis, W. D., & Jones, D. N.) 883–904 (Pergamon Press, 1979).

  • Smith K., in Organometallics in Synthesis: A Manual (ed. Schlosser, M.) 465–533 (Wiley, 2001).

  • Ishida, N., Miura, T. & Murakami, M. Stereoselective synthesis of trisubstituted alkenylboranes by palladium-catalysed reaction of alkynyltriarylborates with aryl halides. Chem. Commun. 4381–4383 (2007).

  • Ishida, N., Shimamoto, Y. & Murakami, M. Stereoselective synthesis of (E)-(trisubstituted alkenyl)borinic esters: stereochemistry reversed by ligand in the palladium-catalyzed reaction of alkynylborates with aryl halides. Org. Lett. 11, 5434–5437 (2009).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Ma, X. et al. Modular assembly of versatile tetrasubstituted alkenyl monohalides from alkynyl tetracoordinate borons. Chem 9, 1164–1181 (2023).

    Article 
    CAS 

    Google Scholar
     

  • Ma, X. et al. Ni-catalysed assembly of axially chiral alkenes from alkynyl tetracoordinate borons via 1,3-metallate shift. Nat. Chem. 16, 42–53 (2024).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Nishihara, Y. et al. Highly regio- and stereoselective synthesis of multialkylated olefins through carbozirconation of alkynylboronates and sequential Negishi and Suzuki–Miyaura coupling reactions. Angew. Chem. Int. Ed. 50, 8660–8664 (2011).

    Article 
    CAS 

    Google Scholar
     

  • Pelter, A., Bentley, T. W., Harrison, C. R., Subrahmanyam, C. & Laub, R. J. The chemistry of organoborates. Part 5. Alkylation of alkynyltrialkylborate salts. J. Chem. Soc. Perkin Trans. 2419–2428 (1976).

  • Sun, S., Jia, Q. & Zhang, Z. Applications of amide isosteres in medicinal chemistry. Bioorg. Med. Chem. Lett. 29, 2535–2550 (2019).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Sun, S. & Fu, J. Methyl-containing pharmaceuticals: methylation in drug design. Bio. Med. Chem. Lett. 28, 3283–3289 (2018).

    Article 
    CAS 

    Google Scholar
     

  • Schmid, G. H. in The Carbon–Carbon Triple Bond (ed. Patai, S.) 275–341 (Wiley, 1978).

  • Soderquist, J. A. & Santiago, B. Methylation via the Suzuki reaction. Tetrahedron Lett. 31, 5541–5542 (1990).

    Article 
    CAS 

    Google Scholar
     

  • Lee, N. R., Linstadt, R. T. H., Gloisten, D. J., Gallou, F. & Lipshutz, B. H. B-alkyl sp3–sp2 Suzuki–Miyaura couplings under mild aqueous micellar conditions. Org. Lett. 20, 2902–2905 (2018).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Tanpure, R. P. et al. Application of the McMurry coupling reaction in the synthesis of tri- and tetra-arylethylene analogues as potential cancer chemotherapeutic agents. Bio. Med. Chem. 17, 6993–7001 (2009).

    Article 
    CAS 

    Google Scholar
     

  • Kirchhoff, J. H., Netherton, M. R., Hills, I. D. & Fu, G. C. Boronic acids: new coupling partners in room-temperature Suzuki reactions of alkyl bromides. Crystallographic characterization of an oxidative-addition adduct generated under remarkably mild conditions. J. Am. Soc. Chem. 124, 13662–13663 (2002).

    Article 
    CAS 

    Google Scholar
     

  • Ozawa, Y., Endo, K. & Ito, H. Regio- and stereoselective synthesis of multi-alkylated allylic boronates through three-component coupling reactions between allenes, alkyl halides, and a diboron reagent. J. Am. Soc. Chem. 143, 13865–13877 (2021).

    Article 
    CAS 

    Google Scholar
     

  • Armstrong, R. J., García-Ruiz, C., Myers, E. L. & Aggarwal, V. K. Stereodivergent olefination of enantioenriched boronic esters. Angew. Chem. Int. Ed. 56, 786–790 (2017).

    Article 
    CAS 

    Google Scholar
     

  • Brown, H. C. et al. Vinylic organoboranes. 13. A convenient stereospecific synthesis of (Z)-1-halo-1-alkenes from 1-alkynes via (E)-1-alkenylborane derivatives with halogens. J. Org. Chem. 54, 6068–6075 (1989).

    Article 
    CAS 

    Google Scholar
     

  • Canterbury, D. P. & Micalizio, G. C. Polyketide assembly by alkene–alkyne reductive cross-coupling: spiroketals through the union of homoallylic alcohols. J. Am. Soc. Chem. 132, 7602–7604 (2010).

    Article 
    CAS 

    Google Scholar
     

  • Soderquist, J. A., Martinez, J., Oyola, Y. & Kock, I. Novel route to carboxylic acids via the DCME reaction. Tetrahedron Lett. 45, 5541–5543 (2004).

    Article 
    CAS 

    Google Scholar
     

  • Corey, E. J. & Seibel, W. L. A simple stereoselective synthesis of Z-γ-bisabolene. Tetrahedron Lett. 27, 909–910 (1986).

    Article 
    CAS 

    Google Scholar
     

  • Jacob, P. III & Brown, H. C. A Grignard-like addition of B-alkenyl-9-borabicyclo[3.3.1]nonanes to aldehydes. A novel synthesis of allylic alcohols with defined stereochemistry. J. Org. Chem. 42, 579–580 (1977).

    Article 
    CAS 

    Google Scholar
     

  • Tandon, N., Luxami, V., Tandon, R. & Paul, K. Recent advances in the synthesis of tamoxifen and analogues in medicinal chemistry. Asian J. Org. Chem. 9, 1432–1465 (2020).

    Article 
    CAS 

    Google Scholar
     

  • Mitra, M. S. & Philip, B. K. in Encyclopedia of Toxicology 3rd edn (ed. Wexler, P.) 143–145 (Academic Press, 2014).

  • Vickery, E. H., Pahler, L. F. & Eisenbraun, E. J. Selective O-demethylation of catechol ethers. Comparison of boron tribromide and iodotrimethylsilane. J. Org. Chem. 44, 4444–4446 (1979).

    Article 
    CAS 

    Google Scholar
     

  • Negishi, E.-i, Zhang, Y. & Bagheri, V. Highly stereoselective synthesis of exocyclic alkenes via cyclialkylation. Tetrahedron Lett. 28, 5793–5796 (1987).

    Article 
    CAS 

    Google Scholar
     

  • Anastasia, L., Dumond, Y. R. & Negishi, E.-i Stereoselective synthesis of exocyclic alkenes by Cu-catalyzed allylmagnesiation, Pd-catalyzed alkylation, and Ru-catalyzed ring-closing metathesis: highly stereoselective synthesis of (Z)- and (E)-γ-bisabolenes. Eur. J. Org. Chem. 2001, 3039–3043 (2001).

    Article 

    Google Scholar
     

  • LaLima, N. J. Jr. & Levy, A. B. Stereospecific route to trisubstituted olefins via organoboranes. J. Org. Chem. 43, 1279–1281 (1978).

    Article 
    CAS 

    Google Scholar
     

  • Manna, S. et al. Stereodivergent Zweifel olefination and its mechanistic dichotomy. Angew. Chem. Int. Ed. 62, e202309136 (2023).

    Article 
    CAS 

    Google Scholar
     

  • Zweifel, G., Fisher, R. P., Snow, J. T. & Whitney, C. C. Convenient synthesis of trans olefins from alkynes via hydroboration-cyanohalogenation. J. Am. Chem. Soc. 94, 6560–6561 (1972).

    Article 
    CAS 

    Google Scholar
     

  • Piers, W. E., Bourke, S. C. & Conroy, K. D. Borinium, borenium, and boronium ions: synthesis, reactivity, and applications. Angew. Chem. Int. Ed. 44, 5016–5036 (2005).

    Article 
    CAS 

    Google Scholar
     

  • Cuenca, A. B. & Fernández, E. Boron-Wittig olefination with gem-bis(boryl)alkanes. Chem. Soc. Rev. 50, 72–86 (2021).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Glendening, E. D., Landis, C. R. & Weinhold, F. NBO 7.0: new vistas in localized and delocalized chemical bonding theory. J. Comput. Chem. 40, 2234–2241 (2019).

    Article 
    CAS 
    PubMed 

    Google Scholar
     

  • Frisch, M. J. et al. Gaussian 16 (Gaussian, Inc., 2016).

  • Neese, F. The ORCA program system. WIREs Comput. Mol. Sci. 2, 73–78 (2012).

    Article 
    CAS 

    Google Scholar
     

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