10.1002/chem.202001952
Chemistry - A European Journal
FULL PAPER
143.1, 141.3, 132.3, 131.2, 128.8, 128.6, 128.54, 128.49, 128.46, 128.1,
125.98, 125.94, 125.7, 39.2, 36.2, 33.7, 32.7, 32.1, 31.7, 29.83, 29.76,
29.7, 29.5, 29.4, 27.4, 22.8, 14.3. IR (film): 3063, 2956, 1699, 1652, 1604,
1464, 1454, 968, 744 cm-1. See Supporting Information for GC/MS data
and COSY spectra.
1463, 1272, 1165, 918, 897, 749, 638 cm-1. HRMS: Calc’d C14H18NO2
(M+H) = 232.1338, found 232.1346.
methyl cyclohex-1-ene-1-carboxylate
&
methyl cyclohex-2-ene-1-
carboxylate (4o): Isolated a mix of regioisomers (63:37) as a colorless oil.
1H NMR (500 MHz, CDCl3): δ [6.99-6.96 (m), 5.87-5.82 (m), 5.77-5.72 (m),
Σ2H], [3.72 (s), 3.69 (s), 3.65 (s), Σ3H], 3.13-3.07 (m, 1H), [2.28-2.22 (m),
2.2-2.15 (m), Σ2H], 2.08-1.95 (m, 1H), 1.95-1.71 (m, 2H), 1.69-1.54 (m,
2H). 13C NMR (126 MHz, CDCl3): δ 175.2, 168.2, 139.9, 129.8, 124.4, 51.9,
51.6, 41.2, 29.2, 25.9, 25.4, 24.8, 24.3, 22.2, 21.6, 20.9. IR (film): 3003,
2944, 1634, 1441, 1224, 1153, 919, 750, 640 cm-1. HRMS: Calc’d C8H13O2
(M+H) = 141.0916, found 141.0921.
cyclohex-1-ene-1-carboxamide & cyclohex-2-ene-1-carboxamide (4p):
Isolated mix of regioisomers (80:20) as an amorphous white solid. 1H NMR
(500 MHz, CDCl3): δ [6.71-6.67 (m), 5.94 (dq), 5.72 (dq), Σ3H], 3.00-2.93
(m, 1H), [2.25-2.20 (m), 2.19-2.14 (m), Σ1H], 2.12-1.97 (m, 1H), 1.96-1.82
(m, 2H), 1.78-1.55 (m, 2H). 13C NMR (126 MHz, CDCl3): δ 177.7, 170.8,
135.3, 132.4, 131.6, 124.6, 42.7, 26.6, 25.6, 25.0, 24.4, 22.2, 21.5, 20.5.
HRMS: Calc’d C7H12NO (M+H) = 126.0919, found = 126.0912. IR (film):
3345, 3182, 2930, 2833, 1662, 1627, 1412, 1208, 1152, 898, 624 cm-1.
(E)-undec-1-en-1-ylcyclopentane
&
undecylidenecyclopentane (4g):
Isolated mix of geometric and regioisomers as a colorless oil. 1H NMR (500
MHz, CDCl3): (80:20 E:Z, >95:5 regioisomer ratio) δ [5.43-5.31 (m) & 5.30-
5.23 (m) Σ2H], [2.73-2.63 (m) & 2.41-2.33 (m) Σ1H], [2.08-2.00 (m) & 1.99-
1.92 (m) Σ2H], 1.79-1.70 (m, 2H), 1.69-1.46 (m, 5H), 1.37-1.18 (m, 19H),
0.93-0.83 (m, 4H). 13C NMR (126 MHz, CDCl3): δ 135.7, 135.4, 128.8,
43.8, 40.6, 38.6, 36.7, 34.2, 33.7, 33.0, 32.3, 30.4, 30.14, 30.12, 30.02,
29.98, 29.8, 29.7, 29.6, 29.2, 27.9, 25.8, 25.6, 25.5, 23.1, 14.5. IR (film):
3054, 2925, 1660, 1467, 1456, 970, 705 cm-1. See Supporting Information
for GC/MS data and COSY spectra.
4'-ethyl-[1,1'-bi(cyclohexan)]-3-ene (4h): Isolated as colorless oil. 1H NMR
(500 MHz, CDCl3): δ 5.66 (m, 2H), 2.11-1.95 (m, 3H), 1.83-1.67 (m, 6H),
1.39-1.29 (m, 1H), 1.27-1.14 (m, 3H), 1.12-1.02 (m, 2H), 1.04-0.91 (m, 2H),
0.87 (m, 5H). 13C NMR (126 MHz, CDCl3): δ 127.3, 127.2, 43.0, 39.9, 39.4,
33.3, 30.2, 30.0, 29.3, 26.4, 26.2. IR (film): 3022, 2960, 1668, 1447, 896,
705 cm-1. See Supporting Information for GCMS data and COSY spectra.
tert-butyl (cyclohex-3-en-1-ylmethyl)carbamate (4i): Isolated as colorless
oil. 1H NMR (500 MHz, CDCl3): δ 5.69-5.60 (m, 2H), 4.61 (broad s, 1H),
5. Acknowledgements
3.09-3.00 (m, 2H), 2.13-1.99 (m, 3H), 1.78-1.64 (m, 3H), 1.44 (s, 9H). 13
C
This work was supported by the National Science Foundation
(CHE-1800147) and the Kansas Bioscience Authority Rising Star
program. Support for the NMR instrumentation was provided by
NSF Academic Research Infrastructure Grant No. 9512331, NIH
Shared Instrumentation Grant No. S10RR024664, and NSF Major
Research Instrumentation Grant No. 0320648.
NMR (126 MHz, CDCl3): δ 127.5, 126.1, 46.4, 34.7, 29.6, 28.8, 26.7, 25.1.
HRMS: Calc’d C12H22O2NNa (M+Na) = 235.1548, found = 235.1560. IR
(film): 3343, 2915, 1689, 1519, 1365, 1206, 1150 cm-1.
cyclohex-3-en-1-ol (4j): Isolated as colorless oil. 1H NMR (500 MHz,
CDCl3): δ 5.70-5.62 (m, 1H), 5.61-5.51 (m, 1H), 3.99-3.91 (m, 1H), 2.42-
2.30 (m, 1H), 2.23-2.06 (m, 2H), 2.05-1.95 (m, 1H), 1.91-1.81 (m, 1H),
1.08-1.54 (m, 2H). 13C NMR (126 MHz, CDCl3): δ 126.9, 124.2, 67.1, 34.5,
31.0, 23.7. IR (film): 3465, 3054, 2987, 1652, 1464, 1421, 1150, 705 cm-1.
HRMS: Calc’d C6H14ON (M+NH4) = 116.1075, found = 116.1070.
cyclohex-3-en-1-yl acetate (4k): Isolated as colorless oil. 1H NMR (500
MHz, CDCl3): δ 5.71-5.65 (m, 1H), 5.59-5.55 (m, 1H), 5.04-4.97 (m, 1H),
2.43-2.33 (m, 1H), 2.21-2.1 (m, 3H), 1.93-1.84 (m, 1H), 1.76-1.67 (m, 1H).
13C NMR (126 MHz, CDCl3): δ 170.9, 126.9, 123.8, 69.9, 30.9, 27.4, 23.4,
21.6. IR (film): 3058, 2990, 1698, 1644, 1422, 1211, 1152, 896, 749 cm-1.
HRMS: Calc’d C8H12O2Na (M+Na) = 163.0735, found = 163.0740.
4'-chloro-1,2,3,6-tetrahydro-1,1'-biphenyl (4l): Isolated as colorless oil. 1H
NMR (500 MHz, CDCl3): δ 7.29 (d, 2H), 7.18 (d, 2H), 5.80-5.76 (m, 2H),
2.85-2.77 (m, 1H), 2.34-2.24 (m, 1H), 2.23-2.08 (m, 3H), 1.96-1.89 (m, 1H),
1.79-1.69 (m, 1H). 13C NMR (126 MHz, CDCl3): δ 145.6, 131.4, 128.3,
128.1, 126.9, 126.4, 39.4, 22.2, 29.5, 25.6. IR (film): 3024, 2914, 1665,
1652, 1464, 824, 668, 643 cm-1. HRMS: Calc’d C10ClH13 (M+H) = 168.0706,
found = 168.0705.
Keywords: dual catalysis • photoredox • cobaloxime •
decarboxylative • hydrogen evolution
6. References
[1]
Reviews: a) H. Huang, K. Jia, Y. Chen, ACS Catal. 2016, 6, 4983-4988.
b) J. Xuan, Z.-G. Zhang, W.-J. Xiao, Angew. Chem., Int. Ed. 2015, 54,
15632−15641. c) R. A. Angnes, Z. Li, C. R. D. Correia, G. B. Hammond,
Org. Biomol. Chem. 2015, 13, 9152−9167. Select examples: d) A.
Tlahuext-Aca, L. Candish, R. A. Garza-Sanchez, F. Glorius, ACS Catal.
2018, 8, 1715−1719. e) K. Xu, Z. Tan, H. Zhang, J. Liu, S. Zhang, Z.
Wang, Chem. Commun. 2017, 53, 10719-10722. f) S. B. Lang, K. C.
Cartwright, R. S. Welter, T. M. Locascio, J. A. Tunge, Eur. J. Org. Chem.
2016, 3331−3334. g) Z. Zuo, D. T. Ahneman, L. Chu, J. A. Terrett, A. G.
Doyle, D. W. C. MacMillian, Science, 2014, 345, 436-440. h) S. Ventre,
F. R. Petronijevic, D. W. MacMillan, J. Am. Chem. Soc. 2015, 137,
5654−5657. i) S. B. Lang, K. M. O’Nele, J. A. Tunge, J. Am. Chem. Soc.
2014, 136, 13606−13609. j) Z. Zuo, D. W. C. MacMillan, J. Am. Chem.
Soc. 2014, 136, 5257−5260. k) Y. Miyake, K. Nakajima, Y. Nishibayashi,
Chem. Commun. 2013, 49, 7854−7856.
tert-butyl cyclohex-2-en-1-ylcarbamate
& tert-butyl cyclohex-3-en-1-
ylcarbamate (4m): Isolated a mix of regioisomers (63:36) as colorless oil.
1H NMR (500 MHz, CDCl3): δ [5.81-5.76 (m) & 5.67-5.62 (m) & 5.59-5.55
(m), Σ2H], [4.5 (broad s) & 3.77 (broad s), Σ1H], 2.41-2.32 (m, 1H), 2.17-
2.07 (m, 1H), 2.01-1.93 (m, 1H), 1.92-1.79 (m, 2H), 1.69-1.58 (m, 1H),
1.58-1.47 (m, 1H), 1.44 (s, 9H). 13C NMR (126 MHz, CDCl3): δ 171.3, 155.5,
130.5, 128.3, 127.1, 124.6, 80.0, 60.5, 45.8, 33.7, 32.2, 29.9, 28.6, 25.7,
24.9, 23.8, 21.2, 19.8, 14.3. IR (film): 3353, 3025, 2978, 1682, 1652, 1464,
1180, 668 cm-1. HRMS: Calc’d C11H19NO2Na (M+Na) = 220.1313, found
220.1314.
[2]
Decarbonylative strategies towards olefins: (a) P. García-Reynaga, A. K.
Carrillo, M. S. VanNieuwenhze Org. Lett. 2012, 14, 1030−1033.
Decarboxylative strategies for olefination: (b) A. B. Miller, Nelson, J. A.
M. P. Byrne, J. Org. Chem. 1993, 58, 18−20. (c) L. J. Gooßen, Rodriguez
N. Chem. Commun. 2004, 0, 724−725. (d) S. Maetani, T. Fukuyama, N.
Suzuki, D. Ishihara, I. Ryu, Organometallics 2011, 30, 1389−1394. (e) S.
Maetani, T. Fukuyama, N. Suzuki, D. Ishihara, I. Ryu, Chem. Commun.
2012, 48, 2552− 2554. (f) M. O. Miranda, A. Pietrangelo, M. A. Hillmyer,
W. B. Tolman Green Chem. 2012, 14, 490−494. (g) R. E. Murray, E. L.
Walter, K. M. Doll, ACS Catal. 2014, 4, 3517−3520. (h) Y. Liu, K. E. Kim,
M. B. Herbert, A. Fedorov, R. H. Grubbs, B. M. Stoltz, Adv. Synth. Catal.
benzyl cyclohex-1-en-1-ylcarbamate
&
benzyl cyclohex-2-en-1-
ylcarbamate (4n): Isolated a mix of regioisomers (95:5) as an amorphous
white solid. 1H NMR (500 MHz, CD3CN): δ 7.47-7.27 (m, 5H), 5.82 (m, 1H),
[5.64 (broad s) & 5.53 (broad s) Σ1H], 5.05 (m, 2H), 4.11 (m, 1H), 2.18 (s,
1H), 2.03-1.96 (m, 1H), 1.89-1.82 (m, 1H), 1.74-1.65 (m, 1H), 1.64-1.55
(m, 1H), 1.55-1.46 (m, 1H), [1.36-1.26 (m) & 1.22-1.11 (m) Σ1H]. 13C NMR
(126 MHz, CD3CN): δ 156.7, 138.5, 130.9, 129.4, 129.1, 128.8, 128.7, 66.7,
47.5, 30.4, 25.4, 20.6. IR (film): 3521, 3061, 3001, 2942, 1716, 1644, 1634,
This article is protected by copyright. All rights reserved.