Synlett 2023; 34(18): 2205-2209
DOI: 10.1055/a-2051-1054
cluster
Modern Boron Chemistry: 60 Years of the Matteson Reaction

Preparation and Use of (γ,γ-Dioxyallyl)boronates

Soshi Nishino
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Yuji Nishii
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
,
Koji Hirano  ∗
a   Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Suita, Osaka 565-0871, Japan
b   Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), Osaka University, Suita, Osaka 565-0871, Japan
› InstitutsangabenThis work was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI Grant JP 22J10951, Grant-in-Aid for JSPS Research Fellow to S.N., and JP 22H02077, Grant-in-Aid for Scientific Research(B) to K.H.) as well as by the Japan Science and Technology Agency (JST) FOREST Program (Grant JPMJFR211X to K.H.).
› Weitere Informationen
    Lizenzen und Reprints Alle Artikel dieser Rubrik


Abstract

A copper-catalyzed stereoselective 1,4-acylboration of α,β-unsaturated esters with B2pin2 and pivalic anhydride has been developed to afford the corresponding (E)-allylboronates with two distinct oxygenated functionalities at the γ positions, which are difficult to prepare by other means. The chemoselective post functionalizations of Bpin and pivalate moieties in the product are also demonstrated.

Key words

allylboronate - borylation - conjugate addition - copper - stereoselectivity

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-2051-1054.
  • Supporting Information


Publikationsverlauf

Eingereicht: 27. Februar 2023

Angenommen nach Revision: 09. März 2023

Accepted Manuscript online:
09. März 2023

Artikel online veröffentlicht:
05. April 2023

© 2023. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 

  • References and Notes

    • 1a Pelter A, Smith K, Brown HC. Borane Reagents . Academic Press; London: 1988
      Google Scholar
    • 1b Miyaura N, Suzuki A. Chem. Rev. 1995; 95: 2457
      CrossrefPubMed
    • 1c Davison M, Hughes AK, Marder TB, Wade K. Contemporary Boron Chemistry . The Royal Society of Chemistry; Cambridge: 2000
      CrossrefGoogle Scholar
    • 1d Boronic Acids, 2nd ed. Hall DG. Wiley-VCH; Weinheim: 2011
      Google Scholar
    • 1e Huo H.-H, Duvall JR, Huang M.-Y, Hong R. Org. Chem. Front. 2014; 1: 303
      Crossref
    • 1f Diner C, Szabó KJ. J. Am. Chem. Soc. 2017; 139: 2
      CrossrefPubMed
    • 1g Clement H, Hall DG. Recent Advances in the Stereoselective Additions of Allylic Boronates to Carbonyl Compounds. In Patai’s Chemistry of Functional Groups. John Wiley & Sons; Hoboken: 2020. DOI: 10.1002/9780470682531.pat0968
      CrossrefGoogle Scholar
    • 2a Hoffmann RW, Kemper B. Tetrahedron Lett. 1981; 22: 5263
      Crossref
    • 2b Wuts PG. M, Bigelow SS. J. Org. Chem. 1982; 47: 2498
      Crossref
    • 2c Brown HC, Jadhav PK, Bhat KS. J. Am. Chem. Soc. 1988; 110: 1535
      Crossref
    • 2d Muñoz-Hernández L, Soderquist JA. Org. Lett. 2009; 11: 2571
      CrossrefPubMed
    • 3a Moriya T, Suzuki A, Miyaura N. Tetrahedron Lett. 1995; 36: 1887
      Crossref
    • 3b Yamamoto Y, Miyairi T, Ohmura T, Miyaura N. J. Org. Chem. 1999; 64: 296
      CrossrefPubMed

      • Hall also reported the related palladium-catalyzed olefin isomerization and consecutive allylic borylation of alkenyl triflates:
    • 3c Lessard S, Peng F, Hall DG. J. Am. Chem. Soc. 2009; 131: 9612
      CrossrefPubMed
  • 4 Gao X, Hall DG. J. Am. Chem. Soc. 2003; 125: 9308
    CrossrefPubMed
    • 5a Yamamoto Y, Takenouchi Y, Ozaki T, Miya T, Ito H. J. Am. Chem. Soc. 2014; 136: 16515
      CrossrefPubMed
    • 5b Takenouchi Y, Kojima R, Momma R, Ito H. Synlett 2017; 28: 270
  • 6 Nishino S, Hirano K. Asian J. Org. Chem. 2023; 12: e202200636
    CrossrefPubMed
  • 7 In the case with (i-PrCO)2O, the Piv group derived from CsOPiv was also incorporated into the product, and the Piv-derived 1,4-acylboration product was also detected in ca. 5% 1H NMR yield. We also tried the reaction with a 1:1 mixture of Piv2O and Ac2O. The corresponding Piv- and Ac-derived 1,4-acylboration products were formed in 21% and 2%, yields, respectively. Additionally, the protoboration byproduct 3a was also detected in 40% yield. Given that 3a mainly arose from the Ac-derived 1,4-acylboration product via in situ hydrolysis, the electrophilic trapping ability of Ac2O is higher than that of Piv2O.
  • 8 We also monitored the reaction progress of 1k in toluene-d 8 by 1H NMR spectroscopy, but 2k′ was the primary product under the catalytic conditions: any acyl migration from 2k to 2k′ was not observed. See the Supporting Information for details and a related paper: Zeng L, Lai Z, Cui S. J. Org. Chem. 2018; 83: 14834
    CrossrefPubMed

      • For pioneering work, see:
    • 9a Ito H, Yamanaka H, Tateiwa J, Hosomi A. Tetrahedron Lett. 2000; 41: 6821
      Crossref
    • 9b Takahashi K, Ishiyama T, Miyaura N. Chem. Lett. 2000; 29: 982
      Crossref

      • For recent reviews, see:
    • 9c Semba K, Fujihara T, Terao J, Tsuji Y. Tetrahedron 2015; 71: 2183
      Crossref
    • 9d Hemming D, Fritzemeier R, Westcott SA, Santos WL, Steel PG. Chem. Soc. Rev. 2018; 47: 7477
      CrossrefPubMed
    • 9e Xue W, Oestreich M. ACS Cent. Sci. 2020; 6: 1070
      CrossrefPubMed
    • 9f Fujihara T. Asian J. Org. Chem. 2022; 11: e202200535
      Crossref
    • 9g Das KK, Mahato S, Hazra S, Panda S. Chem. Rec. 2022; 22: e202100290
      CrossrefPubMed
    • 10a Whiting A. Tetrahedron Lett. 1991; 32: 1503
      Crossref
    • 10b Mears RJ, Whiting A. Tetrahedron 1993; 49: 177
      Crossref
    • 10c Conole G, Mears RJ, De Silva H, Whiting A. J. Chem. Soc., Perkin Trans. 1 1995; 1825
      Crossref
    • 10d Mears RJ, Sailes HE, Watts JP, Whiting A. J. Chem. Soc., Perkin Trans. 1 2000; 3250
      Crossref
    • 10e Sailes HE, Watts JP, Whiting A. J. Chem. Soc., Perkin Trans. 1 2000; 3362
      Crossref
    • 10f Zhan M, Ding Z, Du S, Chen H, Feng C, Xu M, Liu Z, Zhang M, Wu C, Lan Y, Li P. Nat. Commun. 2020; 11: 792
      CrossrefPubMed
    • 10g Zuo Y.-J, Chang X.-T, Hao Z.-M, Zhong C.-M. Org. Biomol. Chem. 2017; 15: 6323
      CrossrefPubMed
    • 10h Zuo Y.-J, Zhong Z, Fan Y, Li X, Chen X, Chang Y, Song R, Fu X, Zhang A, Zhong C.-M. Org. Biomol. Chem. 2018; 16: 9237
      CrossrefPubMed
    • 10i Bi Y.-P, Wang H.-M, Qu H.-Y, Liang X.-C, Zhou Y, Li X.-Y, Xu D, Shen M.-H, Xu H.-D. Org. Biomol. Chem. 2019; 17: 1542
      CrossrefPubMed
    • 10j Larin EM, Loup J, Polishchuk I, Ross RJ, Whyte A, Lautens M. Chem. Sci. 2020; 11: 5716
      CrossrefPubMed
    • 10k Nishino S, Nishii Y, Hirano K. Chem. Sci. 2022; 13: 14387
      CrossrefPubMed
  • 11 McElavin SM. Chem. Rev. 1949; 45: 453
    CrossrefPubMed
  • 12 Matteson DS. Chem. Rev. 1989; 89: 1535
    CrossrefPubMed
  • 13 Yin J, Bai Y, Mao M, Zhu G. J. Org. Chem. 2014; 79: 9179
    CrossrefPubMed
  • 14 Experimental Procedures and Characterization Data Synthesis of 2a (Scheme [4, 0].25 mmol scale) Cu(OAc)2 (4.5 mg, 0.025 mmol), P(3,5-(CF3)2C6H3)3 (33.5 mg, 0.050 mmol), and KOPiv (105.2 mg, 0.75 mmol) were placed in a 20 mL Schlenk tube, which was filled with nitrogen by using the Schlenk technique. CPME (1.0 mL) was then added to the tube, and the suspension was stirred for 15 min at ambient temperature. Bis(pinacolato)diboron (158.7 mg, 0.63 mmol) was then added in one portion, and the resulting solution was stirred at the same temperature. After 5 min, pivalic anhydride (69.8 mg, 0.38 mmol) and methyl (E)-5-phenylpent-2-enoate (1a, 40.5 mg, 0.25 mmol) were added dropwise. The reaction solution was stirred at room temperature for additional 18 h. The resulting mixture was directly filtered through a short pad of neutral alumina and Na2SO4. The filtrate was evaporated in vacuo and purified by silica gel column chromatography on neutral silica gel with hexane/ethyl acetate (20/1 → 10/1, v/v) and GPC (CHCl3) to give 1-methoxy-5-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-1-yl pivalate (2a, 82.5 mg, 0.21 mmol) in 82% yield with >99:1 E/Z ratio. (E)-1-Methoxy-5-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pent-1-en-1-yl pivalate ((E)-2a) 82.5 mg (82%); colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.27–7.23 (m, 2 H), 7.21–7.19 (m, 2 H), 7.15 (t, J = 7.1 Hz, 1 H), 4.34 (d, J = 9.9 Hz, 1 H), 3.55 (s, 3 H), 2.74 (ddd, J = 13.6, 10.5, 5.4 Hz, 1 H), 2.59 (ddd, J = 13.6, 10.4, 6.0 Hz, 1 H), 2.09–2.03 (m, 1 H), 1.89–1.80 (m, 1 H), 1.73–1.65 (m, 1 H), 1.28 (s, 9 H), 1.25 (s, 12 H). 13C{1H} NMR (100 MHz, CDCl3): δ = 176.5, 150.6, 142.9, 128.7, 128.3, 125.6, 98.2, 83.3, 57.1, 39.1, 35.4, 33.4, 27.2, 24.9, 24.8, 20.5 (br). 11B NMR (128 MHz, CDCl3,): δ = 32.7. HRMS (APCI): m/z [M + H]+ calcd for C23H36BO5: 403.2654; found: 403.2666.
  • 15 We preliminarily tested several reported conditions, including simple heating, Sc(OTf)3 catalyst, and ZnBr2 catalyst, for the allylation of benzaldehyde with 2a, 6, and 7. However, the allylic boronates just decomposed, and the corresponding homoallylic alcohols were not detected at all. Additional investigations are still necessary.
  • 16 We preliminarily tried enantioselective conditions using several chiral phosphine ligands. However, the maximum enantiomeric ratio was 75:25 with a phosphoramidite ligand. See the Supporting Information for more details.