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Synlett 2022; 33(03): 288-292
DOI: 10.1055/a-1673-9236
letter

Synthesis of C,N,N-Cyclometalated Gold(III) Complexes with Anionic Amide Ligands

Ryotaro Niizeki
a   Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
,
Kosuke Higashida
a   Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
b   Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan
,
Emna Mejri
a   Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
,
Masaya Sawamura  ∗
a   Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
b   Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan
,
Yohei Shimizu  ∗
a   Department of Chemistry, Faculty of Science, Hokkaido University, Kita 10 Nishi 8, Kita-ku, Sapporo, Hokkaido 060-0810, Japan
b   Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Kita 21 Nishi 10, Kita-ku, Sapporo, Hokkaido 001-0021, Japan
› Author AffiliationsThis work was supported by JSPS KAKENHI Grant Number JP20K15268 in Grant-in-Aid for Young Scientists to K.H., JSPS KAKENHI Grant No. JP20H04797 in Hybrid Catalysis and Grant-in-Aid for Scientific Research (B) (No. JP20H02729) to Y.S.
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Dedicated to Professor Christian Bruneau for his outstanding contribution to catalysis.

Abstract

A series of neutral C,N,N Au(III) complexes were synthesized with N-(8-quinolinyl)benzamide derivatives or chiral N-[2-(1,3-oxazolin-2-yl)phenyl]benzamide derivatives. The convenient synthesis method for the amide ligands, together with their operationally simple complexation by direct C–H auration, permitted changes to both the steric and electronic properties of Au(III) complexes for promoting the catalytic three-component couplings of an aldehyde, an amine, and an alkyne.

Key words

gold(III) complexes - ligands - pincer complexes - catalysts - multicomponent reactions - chiral complexes

Supporting Information

    Supporting information for this article is available online at https://doi.org/10.1055/a-1673-9236.
  • Supporting Information


Publication History

Received: 09 September 2021

Accepted after revision: 19 October 2021

Accepted Manuscript online:
19 October 2021

Article published online:
12 November 2021

© 2021. Thieme. All rights reserved

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  • References and Notes

  • 1 Modern Gold Catalyzed Synthesis . Hashmi AS. K, Toste D. Wiley-VCH; Weinheim: 2012
    Google Scholar
  • 3 Rocchigiani L, Bochmann M. Chem. Rev. 2021; 121: 8364
    CrossrefPubMed
  • 4 Kumar R, Nevado C. Angew. Chem. Int. Ed. 2017; 56: 1994
    CrossrefPubMed
    • 5a Wong K.-H, Cheung K.-K, Chan MC.-W, Che C.-M. Organometallics 1998; 17: 3505
      Crossref
    • 5b To W.-P, Zhou D, Tong GS. M, Cheng G, Yang C, Che C.-M. Angew. Chem. Int. Ed. 2017; 56: 14036
      CrossrefPubMed
    • 6a Chan C.-W, Wong W.-T, Che C.-M. Inorg. Chem. 1994; 33: 1266
      Crossref
    • 6b Liu H.-Q, Cheung T.-C, Peng S.-M, Che C.-M. J. Chem. Soc., Chem. Commun. 1995; 1787
      Crossref
    • 6c Cinellu MA, Zucca A, Stoccoro S, Minghetti G, Manassero M, Sansoni M. J. Chem. Soc., Dalton Trans. 1996; 4217
      Crossref
    • 7a Zaitsev VG, Shavashob D, Dauglies O. J. Am. Chem. Soc. 2005; 127: 13154
      CrossrefPubMed
    • 7b Roy P, Bour JR, Kampf JW, Sanford MS. J. Am. Chem. Soc. 2019; 141: 17382 ; corrigendum: J. Am. Chem. Soc. 2021, 143, 14021
      CrossrefPubMed
    • 7c Rouquet G, Chatani N. Angew. Chem. Int. Ed. 2013; 52: 11726
      CrossrefPubMed
    • 8a Lo VK.-Y, Liu Y, Wong M.-K, Che C.-M. Org. Lett. 2006; 8: 1529
      CrossrefPubMed
    • 8b Wei C, Li C.-J. J. Am. Chem. Soc. 2003; 125: 9584
      CrossrefPubMed
    • 8c Lo VK.-Y, Kung KK.-Y, Wong M.-K, Che C.-M. J. Organomet. Chem. 2009; 694: 583
      Crossref
    • 8d Ko H.-M, Kung KK.-Y, Cui J.-F, Wong M.-K. Chem. Commun. 2013; 49: 8869
      CrossrefPubMed
    • 8e von Wachenfeldt H, Polukeev AV, Loganathan N, Paulsen F, Röse P, Garreau M, Wendt OF, Strand D. Dalton Trans. 2015; 44: 5347
      CrossrefPubMed
    • 8f Price GA, Brisdon AK, Randall S, Lewis E, Whittaker DM, Pritchard RG, Muryn CA, Flower KR, Quayle P. J. Organomet. Chem. 2017; 846: 251
      Crossref
  • 9 CCDC 2107007 and 2115822 contains the supplementary crystallographic data for compounds 2a and 2j, respectively. The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/structures
  • 10 Eppel D, Rudolph M, Rominger F, Hashmi AS. K. ChemSusChem 2020; 13: 1986
    CrossrefPubMed
  • 11 Feuerstein W, Holzer C, Gui X, Neumeier L, Klopper W, Breher F. Chem. Eur. J. 2020; 26: 17156
    CrossrefPubMed
  • 12 Au(III) Complexes 2a–l; General Procedure A sealed tube was charged with amide 1 (0.1 mmol), NaAuCl4·2 H2O (39.8 mg, 0.1 mmol), potassium pivalate (19.6 mg, 0.2 mmol), MeCN (2 mL), and H2O (2 mL). The mixture was stirred overnight at 80 °C and then cooled to r.t. The precipitate was collected by filtration, washed with MeOH, and dried in vacuo. Complex 2a Yellowish-brown solid; yield: 31.1 mg (65%); mp 308.3–309.8 ℃. IR (ATR): 2945, 1647, 1625, 1579, 1504, 1463, 1400, 1381 cm–1. 1H NMR (CDCl3, 400 MHz): δ = 9.14 (d, J = 5.2 Hz, 1 H), 9.03 (d, J = 7.6 Hz, 1 H), 8.48 (d, J = 8.4 Hz, 1 H), 7.82 (d, J = 7.6 Hz, 1 H), 7.65–7.71 (m, 2 H), 7.54 (dd, J = 1.6, 7.6 Hz, 1 H), 7.50 (d, J = 7.2 Hz, 1 H), 7.34 (ddd, J = 1.2, 7.6, 7.6 Hz, 1 H), 7.29 (dd, J = 1.6, 8.0 Hz, 1 H). 13C NMR (100.5 MHz, CDCl3): δ = 174.53, 146.56, 144.90, 144.02, 142.18, 141.19, 139.31, 132.42, 131.04, 130.76, 130.67, 130.41, 128.85, 121.91, 121.41, 120.91. HRMS (FD): m/z [M]+ calcd for C16H10AuClN2O: 478.0147; found: 478.0129. Au(III) Complex 4 In a glove box, a vial equipped with a magnetic stirring bar was charged with complex 2a (47.9 mg, 0.1 mmol), 2,2-diphenylpent-4-en-1-ol (3; 47.7 mg, 0.2 mmol), AgBF4 (19.5 mg, 0.1 mmol), and CH2Cl2 (1 mL), and the mixture was stirred for 14 h at r.t. The solvent was removed under reduced pressure, and the crude product was purified by flash chromatography [silica gel, gradient elution hexane to hexane–EtOAc (9:1)] to give a yellow solid; yield: 31.1 mg (65%); mp 275.8–277.5°C. IR (ATR): 2972, 1625, 1582, 1502, 1466, 1394 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.97 (dd, J = 1.2, 8.4 Hz, 1 H), 8.61 (dd, J = 1.6, 5.2 Hz, 1 H), 8.40 (dd, J = 1.2, 8.4 Hz, 1 H), 7.71–7.75 (m, 1 H), 7.65 (dd, J = 8.0, 8.0 Hz, 1 H), 7.52 (dd, J = 5.2, 8.4 Hz, 1 H), 7.36–7.40 (m, 2 H), 7.28–7.32 (m, 2 H), 7.20–7.28 (m, 9 H), 7.12–7.19 (m, 1 H), 4.59 (ddt, J = 6.4, 6.8, 8.0 Hz, 1 H), 4.44 (d, J = 8.8 Hz, 1 H), 4.39 (d, J = 8.8 Hz, 1 H), 2.88 (dd, J = 6.8, 12.4 Hz, 1 H), 2.59 (dd, J = 8.0, 12.4 Hz, 1 H), 2.00 (d, J = 6.4 Hz, 2 H). 13C NMR (100.5 MHz, CDCl3): δ = 173.39, 146.51, 146.46, 146.08, 144.72, 140.57, 135.52, 131.33, 130.60, 129.95, 128.95, 128.41, 128.37, 127.63, 127.26, 127.07, 126.36, 126.25, 121.42, 121.14, 119.51, 80.28, 56.58, 47.57, 34.88. HRMS (ESI): m/z [M + H]+ calcd for C33H28AuN2O2: 681.1811; found: 681.1827. Alkynyl Au(III) Complex 6s In a glove box, a vial equipped with a magnetic stirring bar was charged with complex 2a (47.9 mg, 0.1 mmol), phenylacetylene (5; 12.3 mg, 0.12 mmol), CuI (22.9 mg, 0.12 mmol), Et3N (12.1 mg, 0.12 mmol), and CH2Cl2 (1 mL), and the mixture was stirred for 14 h at r.t. Workup as above gave a yellow solid; yield: 43.8 mg (81%); mp 290.6–293.5 ℃. IR (ATR): 3053, 2989, 1640, 1594, 1582, 1501, 1487, 1462, 1450, 1441, 1384 cm–1. 1H NMR (400 MHz, CDCl3): δ = 9.24 (dd, J = 1.2, 4.8 Hz, 1 H), 9.02 (dd, J = 1.6, 8.4 Hz, 1 H), 8.50 (dd, J = 1.2, 8.4 Hz, 1 H), 7.94 (dd, J = 1.6, 8.0 Hz, 1 H), 7.65–7.72 (m, 2 H), 7.59–7.64 (m, 3 H), 7.49 (dd, J = 1.2, 8.0 Hz, 1 H), 7.26–7.40 (m, 5 H). 13C NMR (100.5 MHz, CDCl3): δ = 174.94, 148.32, 146.40, 145.12, 144.47, 140.95, 136.20, 133.78, 132.28, 131.84, 131.26, 130.77, 130.04, 128.30, 128.23, 127.51, 125.35, 121.92, 121.70, 120.35, 97.94, 96.44. HRMS (ESI): m/z [M + H]+ calcd for C24H16AuN2O: 545.0923; found: 545.0937. A3 Reaction; General Procedure A vial equipped with a magnetic stirring bar was charged with the appropriate complex 2 (0.005 mmol), 4-bromobenzaldehyde (7; 18.5 mg, 0.1 mmol), piperidine (8; 9.4 mg, 0.11 mmol), and phenylacetylene (5; 15.3 mg, 0.15 mmol). H2O (0.2 mL) was added, and the resulting suspension was stirred for 24 h at 40 ℃ then cooled to r.t. The mixture was extracted with EtOAc (×3) and the combined organic layers were dried (MgSO4). The yield was determined by 1H NMR analysis with 1,1,2,2-tetrachloroethane as internal standard.