10.1002/ejoc.202000416
European Journal of Organic Chemistry
FULL PAPER
Isobenzofuran-1(3H)-one (2x)[58]. White solid (68%, 22.7 mg); 1H NMR
(500 MHz, CDCl3) 5.32 (s, 2H), 7.50 (d, J = 7.2 Hz, 1H), 7.53 (dd, J =
7.4, 7.2 Hz, 1H), 7.68 (dd, J = 7.4, 7.4 Hz, 1H), 7.91 (d, J = 7.4 Hz, 1H);
13C NMR (125 MHz, CDCl3) 69.6, 122.1, 125.69, 125.71, 129.0, 134.0,
146.5, 171.1.
30.2, 31.3, 31.6, 32.0, 32.7, 33.9, 35.1, 35.6, 38.6, 39.6, 40.3, 41.6, 53.6,
55.6, 61.9, 66.8, 80.5, 109.2, 123.8, 171.0, 199.4.
(8S,9S,10R,13R,14S,17R)-10,13-Dimethyl-17-((R)-6-methylheptan-2-
yl)-1,2,6,7,8,9,10,11,12,13,14,15,16,17-tetradecahydro-3H-
cyclopenta[a]phenanthren-3-one (4i)[67]. White solid (96%, 68.6 mg); 1H
NMR (400 MHz, CDCl3) 0.69 (s, 3H), 0.84 (dd, J = 6.9, 1.8 Hz, 6H), 0.89
(d, J = 6.4 Hz, 1H), 0.92-1.14 (m, 9H), 1.16 (s, 3H), 1.21-2.07 (m, 1H),
3,4-Dimethoxybenzaldehyde (2y)[59]. Yellow oil (34%, 14.3 mg); 1H NMR
(500 MHz, CDCl3) 3.95 (s,3H), 3.97 (s, 3H), 6.98 (d, J = 8.0 Hz, 1H), 7.42
(d, J = 1.7 Hz, 1H), 7.46 (dd, J = 8.0, 1.7 Hz, 1H), 9.86 (s,1H); 13C NMR
(125 MHz, CDCl3) 56.0, 56.2, 108.9, 110.3, 126.9, 130.1, 149.6, 154.5,
190.9.
1.76-1.90 (m, 2H), 1.96-2.07 (m, 2H), 2.20-2.47 (m, 4H), 5.70 (s, 1H); 13
C
NMR (100 MHz, CDCl3) 11.9, 17.3, 18.6, 20.9, 22.5, 22.8, 23.7, 24.1,
27.9, 28.1, 32.0, 32.9, 33.9, 35.5, 35.6, 35.7, 36.0, 38.5, 39.4, 39.5, 42.3,
53.7, 55.8, 56.0, 123.7, 171.6, 199.6 .
4-Phenylbutan-2-one (4a)[60]. Transparent oil (88%, 32.6 mg); 1H NMR
(400 MHz, CDCl3) 2.15 (s, 3H), 2.77 (t, J = 8.0 Hz, 2H), 2.90 (t, J = 8.0
Hz, 2H), 7.16-7.22 (m, 3H), 7.25-7.33 (m, 2H); 13C NMR (100 MHz, CDCl3)
29.6, 30.0, 45.1, 126.0, 128.2, 128.4, 140.9, 207.9.
(4-(Hydroxy(phenyl)methyl)phenyl)(phenyl)methanone (6). Yellow oil
(23%, 16.7mg); 1H NMR (500 MHz, CDCl3) 2.37 (br s, 1H), 5.93 (s, 1H),
7.30 (t, J = 7.4 Hz, 1H), 7.35-7.41 (m, 4H), 7.47 (dd, J = 7.4, 6.9 Hz, 2H),
7.52 (d, J = 8.0 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.59 (t, J = 6.9 Hz, 1H),
7.78 (d, J = 6.9 Hz, 4H); 13C NMR (125 MHz, CDCl3) 75.9, 126.2, 126.6,
128.0, 128.2 (2C), 128.7, 130.0, 130.3, 132.4, 137.5, 143.2, 148.2, 196.4;
IR (ATR, / cm-1) 3408, 1646, 1598, 1276, 698; HRMS (DART) Calcd for
C20H17O2 [M+H]+ 289.1229, Found 289.1230.
2-Octanone (4b)[58]. Transparent colorless oil (87%, 28.0 mg); 1H NMR
(500 MHz, CDCl3) 0.87 (t, J = 6.9 Hz, 3H), 1.21-1.33 (m. 6H), 1.50-1.60
(m, 2H), 2.12 (s, 3H), 2.40 (t, J = 7.7 Hz, 2H); 13C NMR (125 MHz, CDCl3)
14.0, 22.5, 23.8, 28.8, 29.8, 31.5, 43.8, 209.4.
1,4-Phenylenebis(phenylmethanone) (7)[68]. White solid (77%, 54.8 mg);
1H NMR (500 MHz, CDCl3) 7.51 (dd, J = 8.3, 7.4 Hz, 4H), 7.62 (tt, J =
7.4, 1.1 Hz, 2H), 7.84 (dd, J = 8.3, 1.1 Hz, 4H), 7.89 (s, 4H); 13C NMR (125
MHz, CDCl3) 128.5, 129.7, 130.1, 132.9, 136.9, 140.6, 196.0.
4-(tert-Butyl)cyclohexan-1-one (4c)[61]. White solid (56%, 21.6 mg); 1H
NMR (400 MHz, CDCl3) 0.91 (s, 9H), 1.37-1.53 (m, 3H), 1.98-2.14 (m,
2H), 2.26-2.45 (m, 4H); 13C NMR (100 MHz, CDCl3) 27.6, 32.4, 41.3,
46.7, 212.7.
Cyclododecanone (4d)[62].White solid (73%, 33.4 mg); 1H NMR (500 MHz,
CDCl3) 1.26-1.30 (m, 14H), 1.67-1.75 (m, 4H), 2.37-2.52 (m, 4H); 13C
NMR (125 MHz, CDCl3) 22.3, 22.5, 24.2, 24.6, 24.7, 40.4, 213.0.
N,N'-diisopropylformimidamide (8). Mixture of E/Z-isomers; Brownish-
white solid (74%, 23.6 mg); H NMR (500 MHz, CDCl3) 1.13 (d, J = 6.3
1
Hz, 12H), 1.33 (d, J = 6.9 Hz, 12H), 3.66 (br s, 1H+1H), 3.83 (sept., J =
6.3 Hz, 1H), 4.18 (br s, 1H), 7.51 (br s, 2H); 13C NMR (125 MHz, CDCl3)
23.1, 23.5, 42.2, 50.0, 152.7, 156.9; IR (ATR, / cm-1) 2964, 2938, 2837,
1687, 1384, 1154, 1134, 804; HRMS (DART) Calcd for C7H17N2 [M+H]+
129.1392, Found 129.1396.
Adamantan-2-one (4e)[63]. White solid (62%, 23.2 mg); 1H NMR (500 MHz,
CDCl3) 1.89-2.10 (m, 12H), 2.52 (br s, 2H); 13C NMR (125 MHz, CDCl3)
27.4, 36.2, 39.2, 46.9, 218.5.
Supporting Information (see footnote on the first page of this article):
Copies of 1H and 13C NMR spectra of for dehydrogenation products 2a-x,
4a-i, 6, 7 and amidine 8; kinetic studies including Hammett plot; NMR
experiment for observation of ruthenium hydride species; and additional
optimization of reaction conditions not mentioned in the text (PDF).
(8R,9S,13S,14S)-3-Methoxy-13-methyl-6,7,8,9,11,12,13,14,15,16-
decahydro-17H-cyclopenta[a]phenanthren-17-one (4f)[64]. White solid
(96%, 68.6 mg); 1H NMR (400 MHz, CDCl3) 0.92 (s, 3H), 1.36-1.71 (m,
6H), 1.90-2.31 (m, 5H), 2.36-2.57 (m, 2H), 2.84-2.98 (m, 2H), 3.79 (s, 3H),
6.66 (d, J = 2.7 Hz, 1H), 6.73 (dd, J = 8.5, 2.7 Hz, 1H), 7.21 (d, J = 8.5 Hz,
1H); 13C NMR (100 MHz, CDCl3) 13.8, 21.5, 25.8, 26.5, 29.5, 31.5, 35.8,
38.3, 43.9, 47.9, 50.3, 55.1, 111.5, 113.8, 126.3, 131.9, 137.7, 157.5,
220.9.
Acknowledgements
Methyl
(2S,4aS,6aS,6bR,8aR,12aS,12bR,14bR)-2,4a,6a,6b,9,9,12a-
This work was supported in part by JSPS KAKENHI Grant
Numbers JP18K05110. We thank Prof. Akiko Inagaki at Tokyo
Metropolitan University for her fruitful discussion for NMR
observation of ruthenium hydride species.
heptamethyl-10,13-dioxo-1,2,3,4,4a,5,6,6a,6b,7,8,8a,9,10,11,12,12a,
12b,13,14b-icosahydropicene-2-carboxylate (4g)[65]. White solid (74%,
89.1 mg); H NMR (500 MHz, CDCl3) 0.79 (s, 3H), 0.98-1.03 (m, 1H),
1
1.04 (s, 3H), 1.08 (s, 3H), 1.12 (s, 3H), 1.14 (s, 3H), 1.16-1.21 (m, 1H),
1.24 (s, 3H), 1.26-1.31 (m, 3H), 1.35 (s, 3H), 1.36-1.45 (m, 3H), 1.51-1.61
(m, 3H), 1.64-1.70 (m, 1H), 1.79-1.85 (m, 1H), 1.88-1.92 (m, 1H), 1.96-
2.04 (m, 2H), 2.06-2.10 (m, 1H), 2.31-2.36 (m, 1H), 2.42 (s, 1H), 2.57-2.64
(m, 1H), 2.91-2.96 (m, 1H), 3.67 (s, 3H), 5.68 (s, 1H); 13C NMR (125 MHz,
CDCl3) 15.6, 18.4, 18.7, 21.3, 23.3, 26.3, 26.4, 28.2, 28.5, 31.0, 31.8,
32.0, 34.2, 36.6, 37.7, 39.7, 41.1, 43.2, 44.0, 45.1, 47.7, 48.3, 51.7, 55.3,
61.0, 128.4, 169.7, 176.8, 199.4, 217.1.
Keywords: Ruthenium • Dehydrogenation • Carbodiimide •
Oxidation• Hydrogen Acceptor
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(5'R,6aR,6bS,8aS,9S,10R,12aS,12bS)-5',6a,8a,9-Tetramethyl-1,3',4',
5,5',6,6a,6b,6',7,8,8a,8b,9,11a,12,12a,12b-octadecahydrospiro-
[naphtho[2',1':4,5]indeno[2,1-b]furan-10,2'-pyran]-4(2H)-one (4h)[66]
White solid (75%, 77.2 mg); 1H NMR (500 MHz, CDCl3) 0.78 (d, J = 6.6
Hz, 3H), 0.81 (s, 3H), 0.91-1.00 (m, 4H), 1.02-1.17 (m, 3H), 1.19 (s, 3H),
1.27-1.34 (m, 1H), 1.38-1.48 (m, 2H), 1.50-1.55 (m, 1H), 1.58-1.79 (m, 8H),
1.83-1.89 (m, 2H), 1.99-2.04 (m, 2H), 2.24-2.45 (m, 4H), 3.36 (dd, J = 10.9,
10.9 Hz, 1H), 3.45-3.48 (m, 1H), 4.40 (ddd, J = 15.5, 6.6, 6.6 Hz, 1H), 5.72
(s, 1H); 13C NMR (125 MHz, CDCl3) 14.4, 16.3, 17.1, 17.3, 20.7, 28.7,
[2]
.
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