Synlett 2021; 32(17): 1762-1766
DOI: 10.1055/a-1550-7935
letter

Ni-Catalyzed Reductive Carbonylation of Alkyl Halides to Form Dialkyl Ketones Using Diphenyl Oxalate as CO Surrogate

Yuren Sun
,
Lei Su
,
Weiqi Tong
,
Ken Yao
,
Hegui Gong
National Natural Science Foundation of China (Grant No. 21871173).


Abstract

In this work, we disclosed that diphenyl oxalate serves as a CO surrogate to enable a Ni-catalyzed carbonylation of alkyl bromides/tosylates to afford dialkyl ketones. The reaction shows broad substrate scope and good functional group tolerance.

Supporting Information



Publication History

Received: 23 May 2021

Accepted after revision: 14 July 2021

Accepted Manuscript online:
14 July 2021

Article published online:
30 July 2021

© 2021. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

 
  • References and Notes


    • Selected reviews on carbonylation reaction of alkyl halide:
    • 1a Ryu I, Sonoda N. Chem. Rev. 1996; 96: 177
    • 1b Ryu I, Sonoda N. Angew. Chem., Int. Ed. Engl. 1996; 35: 1050
    • 1c Ryu I. Chem. Soc. Rev. 2001; 30: 16
    • 1d Frish AC, Beller M. Angew. Chem. Int. Ed. 2005; 44: 674
    • 1e Wu L, Fang X, Liu Q, Jackstell R, Beller M, Wu X. -F. ACS Catal. 2014; 4: 2977
    • 1f Sumino S, Fusano A, Fukuyama T, Ryu I. Acc. Chem. Res. 2014; 47: 1563
    • 1g Li Y, Hu Y, Wu X.-F. Chem. Soc. Rev. 2018; 47: 172
    • 2a Kondo T, Tsuji Y, Watanabe Y. Tetrahedron Lett. 1988; 29: 3833
    • 2b Nagahara K, Ryu I, Komatsu M, Sonoda N. J. Am. Chem. Soc. 1997; 119: 5465
    • 2c Tsunoi S, Ryu I, Okuda T, Tanaka M, Komatsu M, Sonoda N. J. Am. Chem. Soc. 1998; 120: 8692

    • Xe irradiation carbonylation at 45 atm:
    • 2d Fukuyama T, Nishitani S, Inouye T, Morimoto K, Ryu I. Org. Lett. 2006; 8: 1383
  • 3 Sargent BT, Alexanian EJ. J. Am. Chem. Soc. 2016; 138: 7520
    • 4a Cheng L.-J, Mankad NP. Acc. Chem. Res. 2021; 54: 2261
    • 4b Cheng L.-J, Mankad NP. J. Am. Chem. Soc. 2017; 139: 10200
    • 4c Cheng L.-J, Islam SM, Mankad NP. J. Am. Chem. Soc. 2018; 140: 1159
    • 4d Cheng L.-J, Mankad NP. Angew. Chem. Int. Ed. 2018; 57: 10328
    • 4e Pye DR, Cheng L.-J, Mankad NP. Chem. Sci. 2017; 8: 4750
    • 4f Zhao S, Mankad NP. Angew. Chem. Int. Ed. 2018; 57: 5867
    • 5a Li Y, Dong K, Zhu F, Wang Z, Wu X.-F. Angew. Chem. Int. Ed. 2016; 55: 7227
    • 5b Li Y, Wang C, Zhu F, Wang Z, Dixneuf PH, Wu X.-F. ChemSusChem 2017; 10: 1341
    • 5c Li Y, Wu X.-F. Commun. Chem. 2018; 1: 39
  • 6 Chen Y, Lei S, Gong H. Org. Lett. 2019; 21: 4689

    • For cobalt-catalzyed carbonylation, see:
    • 7a Sargent BT, Alexanian EJ. J. Am. Chem. Soc. 2017; 139: 12438
    • 7b Cash D, Combs A, Dragojlovic V. Tetrahedron Lett. 2004; 45: 1143
  • 8 McMahon CM, Renn MS, Alexanian EJ. Org. Lett. 2016; 18: 4148

    • For early examples of Ni-mediated carbonylation, see:
    • 9a Heck RF. J. Am. Chem. Soc. 1963; 85: 2013
    • 9b Corey EJ, Hegedus LS. J. Am. Chem. Soc. 1969; 91: 1233
  • 10 Cheng R, Zhao H.-Y, Zhang S, Zhang X. ACS Catal. 2020; 10: 36
    • 11a Shi R, Hu X. Angew. Chem. Int. Ed. 2019; 58: 7454

    • For an early example using chlorofomate as CO source, see:
    • 11b Rérat A, Michon C, Agbossou-Niedercorn F, Gosmini C. Eur. J. Org. Chem. 2016; 4554
  • 12 Wotal AC, Ribson RD, Weix DJ. Organometallics 2014; 33: 5874
  • 13 See the Supporting Information for details.
  • 14 The general procedure as well as the analytical data of a few typical compounds are summarized as follows. Method A To a flame-dried Schlenk tube was charged with alkyl bromide (0.3 mmol, 100 mol%, if it is a solid), diphenyl oxalate (73.0 mg, 0.3 mmol, 100 mol%), Zn (58 mg, 0.90 mmol, 300 mol%), NiBr2 (6.5 mg, 0.03 mmol, 10 mol%), 4,4′-di-tert-butyl-2,2′-bipyridine (16 mg, 0.06 mmol, 20 mol%), MgCl2 (21 mg, 0.225 mmol, 75 mol%). The tube was capped with a rubber septum. After being evacuated and backfilled nitrogen three times, alkyl bromide (0.3 mmol, 100 mol%, if it is a liquid), pyridine (12.0 mg, 0.15 mmol, 50 mol%), and/or TMSBr (23.0 mg, 0.15 mmol, 50 mol%, only for primary bromide) were added followed by addition of DMA (2.0 mL) via syringes. The reaction mixture was allowed to stir for 12 h under a N2 atmosphere at room temperature (25 °C) and was directly loaded onto a silica column without workup. The residue was rinsed with small amount of DCM or the eluent prior to column chromatography and additional preparative TLC separation, with which the product was isolated. Method B To a flame-dried Schlenk tube was charged with alkyl 4-methylbenzenesulfonate (0.3 mmol, 100 mol%, if solid), diphenyl oxalate (73 mg, 0.3 mmol, 100 mol%), Zn (58 mg, 0.90 mmol, 300 mol%), NiI2 (9.4 mg, 0.03 mmol, 10 mol%), 4,4′-di-tert-butyl-2,2′-bipyridine (16 mg, 0.06 mmol, 20 mol%), MgCl2 (21 mg, 0.225 mmol, 75 mol%), KI (50 mg, 0.3 mmol, 100 mol%). The tube was capped with a rubber septum. After being evacuated and backfilled nitrogen three times, alkyl 4-methylbenzenesulfonate (0.3 mmol, 100 mol%, if it is a liquid) was added via a syringe followed by addition of DMA (2.0 mL) via a syringe. The reaction mixture was allowed to stir for 24 h under a N2 atmosphere at 50 °C and was directly loaded onto a silica column without workup. The residue was rinsed with small amount of DCM or the eluent prior to column chromatography and additional preparative TLC separation, with which the product was isolated. 3,5-Dimethyl-1,7-diphenylheptan-4-one (3) Compound 3was prepared according to the method A using (3-bromobutyl)benzene (63.9 mg, 0.3 mmol, 100 mol%). Flash column chromatography (SiO2: 10% ethyl acetate in petroleum ether) gave a colorless oil (37.5 mg, 0.128 mmol, 85% yield). 1H NMR (600 MHz, CDCl3): δ = 7.26 (td, J = 7.5, 3.4 Hz, 4 H), 7.18–7.12 (m, 6 H), 2.64 (hept, J = 6.8 Hz, 2 H), 2.58–2.52 (m, 4 H), 2.03–1.94 (m, 2 H), 1.63–1.55 (m, 2 H), 1.08 (dd, J = 10.2, 6.9 Hz, 6 H). 13C NMR (151 MHz, CDCl3): δ = 217.59, 217.44, 141.88, 141.81, 128.50, 128.49, 128.42, 126.02, 126.01, 44.55, 44.46, 34.42, 33.64, 33.54, 16.71, 16.64. HRMS (ESI): m/z calcd for [M + Na+] (C21H26ONa+): 317.1876; found: 317.1881.
  • 15 The bond energy of the C–C bond within phenyl oxalate is unknown. However, we noticed that in a discussion of radical-mediated C–C cleavage of unstrained cycloketones by Zhu et al. the energy barrier for cleavage of Csp3–Csp3 bond involving a ketyl radical is approximately 6.6 kcal/mol. We speculate that phenyl oxalate may require less energy barrier than that in Zhu’s case, which deals with Csp2–Csp3 bond cleavage, see: Wang M, Li M, Yang S, Xue X.-S, Wu X, Zhu C. Nat. Commun. 2020; 11: 672
  • 16 In addition, a summary of BDE in a website suggests that the C(O)–C(O) bond within methyl oxalate possesses a BDE of 88 kcal/mol, see (accessed July 25 2021): http://iBonD.nankai.edu.cn.
    • 17a Liu J, Ye Y, Sessler JL, Gong H. Acc. Chem. Res. 2020; 53: 1833
    • 17b Biswas, S.; Weix, D. J. J. Am. Chem. Soc.; 2013, 135: 161, 92.