10.1002/cctc.202001464
ChemCatChem
FULL PAPER
mmol), 2-(2-methoxyphenyl)-5,5-dimethyl-2-phenyl-1,3,2-dioxaborinane
(220 mg, 1.00 mmol), potassium carbonate (207 mg, 1.50 mmol) and
PhS-IPent-CYP (0.06 mg, 0.06 µmol), the product was obtained in 92 %
yield (140.9 mg, 0.458 mmol) as a colorless liquid. 1H NMR (300 MHz,
CDCl3, ppm): δ 1.47 (s, 9H), 1.94–1.97 (m, 4H), 3.30 (brs, 2H), 3.87 (s,
3H), 4.00 (brs, 2H), 4.08 (brs, 1H), 6.91–6.97 (m, 2H), 7.21–7.28 (m, 2H);
13C NMR (75 MHz, CDCl3, ppm): δ 28.5, 35.9, 39.5, 55.3, 71.3, 79.2,
111.4, 121.1, 125.5, 128.4, 134.7, 155.0, 157.1.
Keywords: 1,2-Addition • Benzylic Alcohols • Carbene Ligands •
Cyclometallated Complexes • Palladium
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tert-Butyl
4-(4-fluorophenyl)-4-hydroxypiperidine-1-carboxylate
(7g).[5d] Using tert-butyl 4-oxopiperidine-1-carboxylate (100 mg, 0.50
mmol), 2-(4-fluorophenyl)-5,5-dimethyl-1,3-2-dioxaborinane(208 mg, 1.00
mmol), potassium carbonate (207 mg, 1.50 mmol) and PhS-IPent-CYP
(0.12 mg, 0.09 µmol), the product was obtained in 97 % yield (143.9 mg,
0.487 mmol) as a white solid; mp 105–106 °C; 1H NMR (300 MHz, CDCl3,
ppm): δ 1.43 (s, 9H), 1.68 (d, J = 12.7 , 2H), 1.84–1.93 (m, 2H), 2.81 (s,
1H), 3.19 (brs, 2H), 3.93 (d, J = 12.5 , 2H), 6.96–7.03 (m, 2H), 7.39–7.44
(m, 2H); 13C NMR (75 MHz, CDCl3, ppm): δ 28.4, 38.1, 39.7, 70.9, 79.7,
115.0 (d, J = 21.1 Hz), 126.3 (d, J = 7.9 Hz), 144.2 (d, J = 3.0 Hz), 154.9,
161.8 (d, J = 244 Hz);19F NMR (376MHz, CDCl3, ppm): δ -114.0.
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For selected reviews, see: a) Y.-L. Liu, X.-T. Lin, Adv. Synth. Catal.
2019, 361, 876–918; b) S. Mondal, D. Roy, G. Panda, Tetrahedron
2018, 74, 4619–4703; c) H. Pellissier, Tetrahedron 2015, 71, 2487–
2524; d) M. Schlosser, in: Organometallics in Synthesis (Ed.: M.
Schlosser), Wiley, Hoboken, 2013, pp 107–111; e) X.-F. Wu, H.
Neumann, Adv. Synth. Catal. 2012, 354, 3141–3160; f) C. M. Binder, B.
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For selected reviews, see: a) W. Li, J. Zhang, Adv. Organomet. Chem.
2020, 74, 325–403; b) A. J. Burke, C. S. Marques, Catalytic Arylation
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Weinheim, 2015, pp 329–375; c) Y.-w. Sun, P.-l. Zhu, Q. Xu, M. Shi,
RSC Adv. 2013, 3, 3153–3168; d) D. V. Partyka, Chem. Rev. 2011, 111,
1529–1595.
tert-Butyl
carboxylate (7h).[5d] Using tert-butyl 4-oxopiperidine-1-carboxylate (100
mg, 0.50 mmol), 5,5-dimethyl-2-(-(trifluoromethyl)phenyl)-1,3,2-
4hydroxy-4-(4-(trifluoromethyl)phenyl)piperidine-1-
dioxaborinane (258 mg, 1.00 mmol), potassium carbonate (207 mg, 1.50
mmol) and PhS-IPent-CYP (0.31 mg, 0.25 µmol), the product was
obtained in 85 % yield (147.5 mg, 0.427 mmol) as a white solid; 146–
147 °C; 1H NMR (300 MHz, CDCl3, ppm): δ 1.46 (s, 9H), 1.71 (d, J = 12.4
Hz, 2H), 1.91–2.00 (m, 2H), 2.67 (s, 1H), 3.20 (brs, 2H), 4.01 (d, J = 12.0
Hz, 2H), 7.61 (s, 4H); 13C NMR (75 MHz, CDCl3, ppm): δ 28.4, 37.9, 39.7,
71.4, 79.8, 124.1 (q, J = 270 Hz), 125.1, 125.3 (q, J = 3.7 Hz), 129.3 (q, J
= 32.2 Hz), 152.2, 154.9;19F NMR(376MHz, CDCl3, ppm): δ -62.5.
For selected recent examples with Rh catalysts, see: a) C.-A. Chang,
T.-Y. Uang, J.-H. Jian, M.-Y. Zhou, M.-L. Chen, T.-S. Kuo, P.-Y. Wu,
H.-L. Wu, Adv. Synth. Catal. 2018, 360, 3381–3390; b) L. G. Borrego,
R. Recio, M. Alcarranza, N. Khiar, I. Fernández, Adv. Synth. Catal.
2018, 360, 1273–1279; c) M. Veguillas, J. Rojas-Martín, M. Ribagorda,
M. C. Carreño, Org. Biomol. Chem. 2017, 15, 5386–5394; d) L. S.
Dobson, G. Pattison, Chem. Commun. 2016, 52, 11116–11119; e) D.-X.
Zhu, W.-W. Chen, M.-H. Xu, Tetrahedron 2016, 72, 2637–2642; f) L.
Huang, J. Zhu, G. Jiao, Z. Wang, X. Yu, W.-P. Deng, W. Tang, Angew.
Chem. Int. Ed. 2016, 55, 4527–4531; Angew. Chem. 2016, 128, 4603–
607; g) C. S. Marques, D. Peixoto, A. J. Burke, RSC Adv. 2015, 5,
20108–20114; h) J. Yang, X. Chen, Z. Wang, Tetrahedron Lett. 2015,
56, 5673–5675; i) C. Zhang, J. Yun, Org. Lett. 2013, 15, 3416–3419; j)
D. W. Low, G. Pattison, M. D. Wieczysty, G. H. Churchill, H. W. Lam,
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Org. Lett. 2012, 14, 1544–1547; l) C.-H. Xing, Y.-X. Liao, P. He, Q.-S.
Hu, Chem. Commun. 2010, 46, 3010–3012; m) J. Jacq, B. Bessières, C.
Einhorn, J. Einhorn, Org. Biomol. Chem. 2010, 8, 4927–4933. n) A. F.
Trindade, V. Andre, M. T. Duarte, L. F. Veiros, P. M. P. Gois, C. A. M.
Afonso, Tetrahedron 2010, 66, 8494–8502.
tert-butyl
4-hydroxy-4-(3-methoxycarbonyl)phenyl)piperidine-1-
carboxylate (7i). Using tert-butyl 4-oxopiperidine-1-carboxylate (100 mg,
0.50 mmol), methyl 3-(5,5-dimethyl-1,3,2-dioxaborinan-2-yl)benzoate(248
mg, 1.00 mmol), potassium carbonate (207 mg, 1.50 mmol) and PhS-
IPent-CYP (0.31 mg, 0.25 µmol), the product was obtained in 93 % yield
(156.2 mg, 0.466 mmol) as a white solid. mp 119–120 °C;1H NMR (300
MHz, CDCl3, ppm): δ 1.44 (s, 9H), 1.71(d, J = 12.6 Hz, 2H), 1.90–2.00 (m,
2H), 2.81 (s, 1H), 3.22 (brs, 2H), 3.86 (s, 3H), 3.98 (d, J = 12.1 Hz, 2H),
7.39 (t, J = 7.8 Hz, 1H), 7.68 (m, 1H), 7.88 (m, 1H), 8.12 (m, 1H); 13
C
NMR (75 MHz, CDCl3, ppm): δ 28.4, 38.0, 40.0, 52.1, 71.3, 79.6, 125.8,
128.3, 128.5, 129.3, 130.1, 148.8, 154.8, 167.1; FTMS (APCl) m/z: [M-
H]+ calcd. For C18H24O5N:334.1660. Found: 334.1668.
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H. Cui, T. Li, J. Ma, H. Cao, Lett. Org. Chem. 2020, 17, 248–253; b) S.
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A 2012, 365, 95–102; d) C. Berini, O. Navarro, Chem. Commun. 2012,
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tert-butyl 4-hydroxy-4-(3-nitrophenyl)piperidine-1-carboxylate (7j).
Using a mixture of tert-butyl 4-oxopiperidine-1-carboxylate (100 mg, 0.50
mmol), 5,5-dimethyl-2-(3-nitrophenyl)-1,3-2-dioxaborinane (235 mg, 1.00
mmol), potassium carbonate (207 mg, 1.50 mmol) and PhS-IPent-CYP
(0.91 mg, 0.74 µmol), the product was obtained in 90 % yield (144.3 mg,
0.448 mmol) as a yellow liquid.;1H NMR (300 MHz, CDCl3, ppm): δ 1.39
(s, 9H), 1.71 (d, J = 12.7, 2H), 1.90–1.97 (m, 2H), 3.21 (brs, 2H), 3.57 (s,
1H) 3.95–3.99 (m, 2H), 7.48 (t, J = 8.0 Hz, 1H), 7.78 (m, 1H), 8.03 (m,
1H), 8.36 (t, J = 2.0 , 1H); 13C NMR (75 MHz, CDCl3, ppm): δ 28.4, 37.9,
39.7, 71.2, 79.9, 120.0, 122.0, 129.3, 131.1, 148.2, 150.9, 154.8; FTMS
(APCl) m/z: [M-H]+ calcd. For C16H21O5N2:321.1456. Found: 321.1461.
Acknowledgements
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a) R. Akiyama, M. Sugaya, H. Shinozaki, T. Yamamoto, Synth.
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We thank Prof. Oe, Doshisha University and Prof. Mino, Chiba
University, for the HRMS measurements. This work was
supported in part by the Research Institute for Science and
Technology, Tokyo Denki University Grant Number Q19E-06.
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