E
Synlett
A. Bhatia, S. Muthaiah
Letter
(
3) (a) Sheldon, R. A.; Kochi, J. K. Metal-Catalyzed Oxidations of
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(
2
c) Li, H.; Lu, G.; Jiang, J.; Huang, F.; Wang, Z.-X. Organometallics
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Catal. A: Chem. 2002, 189, 119.
(
4) (a) Murahashi, S.; Naota, T.; Ito, K.; Maeda, Y.; Taki, H. J. Org.
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3
1
479. (c) Gunanathan, C.; Milstein, D. Science 2013, 341,
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Gonsalvi, L.; Laurenczy, G.; Peruzzini, M. Appl. Organomet.
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Rev. 2010, 39, 81; and references cited therein. (e) Vicent, C.;
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Technol. 2017, 7, 1654.
(5) (a) Kawahara, R.; Fujita, K.-I.; Yamaguchi, R. J. Am. Chem. Soc.
(15) [RuCl (PPh ) (2-PyCH PTA)]·Br (2)
2
3
2
2
2
012, 134, 3643. (b) Fujita, K.-I.; Tamura, R.; Tanaka, Y.; Yoshida,
M.; Onoda, M.; Yamguchi, R. ACS Catal. 2017, 7, 7226.
c) Maenaka, Y.; Suenobu, T.; Fukuzumi, S. J. Am. Chem. Soc.
012, 134, 9417. (d) Wang, X.; Wang, C.; Liu, Y.; Xiao, J. Green
In an oven-dried Schlenk flask, [2-PyCH PTA]·Br (1; 0.329 g, 1
2
mmol) was added to a solution of RuCl (PPh ) (0.881 g, 1
2
3 3
(
2
mmol) in toluene (~50 mL). The resulting mixture was refluxed
for ~12 h then cooled and filtered. The brown residue was
washed with hexane and dried under vacuo to obtain the ana-
lytically pure product as a free flowing brown solid; yield: 0.860
Chem. 2016, 18, 4605.
(
6) (a) Balaraman, E.; Khaskin, E.; Leitus, G.; Milstein, D. Nat. Chem.
2
013, 5, 122. (b) Sponholz, P.; Mellmann, D.; Cordes, C.;
g (90%).
1
Alsabeh, P. G.; Li, B.; Li, Y.; Nielsen, M.; Junge, H.; Dixneuf, P.;
Beller, M. ChemSusChem 2014, 7, 2419. (c) Choi, J.-H.; Heim, L.
E.; Ahrens, M.; Prechtl, M. H. G. Dalton Trans. 2014, 43, 17248.
H NMR (300 MHz, CDCl , 25 °C): δ = 2.47 (d, J = 16 Hz, 2 H,
3
PCH H N), 2.88 (d, J = 16 Hz, 2 H, PCH H N), 2.98 (d, J = 12 Hz, 2
A
B
A
B
+
H, PCH N ), 3.11 (s, 1 H, NCH H N), 3.55 (s, 1 H, NCH H N), 4.31
2
A
B
A
B
+
+
(
d) Zhang, L.; Nguyen, D. H.; Raffa, G.; Trivelli, X.; Capet, F.;
Desset, S.; Paul, S.; Dumeignil, F.; Gauvin, R. M. ChemSusChem
016, 9, 1413.
(s, 2 H, N CH C ), 5.09 (d, J = 12 Hz, 2 H, N CH H N), 5.24 (d, J =
12 Hz, 2 H, N CH H N), 7.16–7.21 (m, 30 H, PPh ; 1 H, Hpy), 7.67
(t, J = 8 Hz, 1 H, Hpy), 8.51 (d, J = Hz, 2 H, Hpy). C{ H} NMR (300
MHz, DMSO-d , 25 °C): δ = 49.88 (d, J = 52 Hz, PCH N); 54.09
(d, JPC = 52 Hz, PCH N ); 68.42 (s, pyCH N ); 72.03 (s, NCH N);
2
p
y
A
B
+
A
B
3
13
1
2
(
(
7) Bhatia, A.; Muthaiah, S. ChemistrySelect 2018, 3, 3737.
8) (a) Pinault, N.; Bruce, D. W. Coord. Chem. Rev. 2003, 241, 1.
6
P–C
2
+
+
2
2
2
+
(b) Verspui, G.; Feiken, J.; Papadogianakis, G.; Sheldon, R. A. J. Mol.
73.36 (s, NCH N ); 128.68 (s, Cpy); 131.41 (s, Cpy); 133.17 (d, JPC =
2
Catal. A: Chem. 1999, 146, 299. (c) Herrmann, W. A.;
Kohlpaintner, C. W. Angew. Chem. Int. Ed. Engl. 1993, 32, 1524.
36 Hz, CPh); 136.47 (s, Cpy); 141.11 (s, CPh); 144.99 (s, Cpy);
31
1
151.83 (s, Cpy). P{ H} NMR (300 MHz, DMSO-d ): δ = –26.68 (t,
6
(
d) Mika, L. T.; Orha, L.; van Driessche, E.; Garton, R.; Zih-
Perényi, K.; Horváth, I. T. Organometallics 2013, 32, 5326.
e) Ding, H.; Bunn, B. B.; Hanson, B. E. Inorg. Synth. 1998, 32, 29.
f) Verkade, J. G. Coord. Chem. Rev. 1994, 137, 233. (g) Zablocka,
JP–P = 36 Hz, Ru-PTA), 29.22 (d, J = 36 Hz, Ru-PPh ). ESI-MS
P–P
3
+
(+ve): m/z = 945.31 [M] . Anal. Calcd for C48H48BrCl N P Ru: C
2
4 3
(
(
56.21, H 4.72, N 5.46. Found: C 56.17, H 4.70, N 5.41.
(16) Dehydrogenation of Alcohols; General Procedure
M.; Hameau, A. L.; Caminade, A.-M.; Majoral, J.-P. Adv. Synth.
Catal. 2010, 352, 2341. (h) McAuliffe, C. A. In Comprehensive
Coordination Chemistry: The Synthesis, Reactions, Properties and
Applications of Coordination Compounds; Wilkinson, G.; Gillard,
R. D.; McCleverty, J., Eds.; Pergamon: Oxford, 1987, Chap. 14
A Schlenk tube was charged with Ru complex 2 (5 mol%), base
(15 mol%), the appropriate alcohol (5 mmol), and H O (1.0 mL),
2
and the mixture was stirred under reflux for 48 h. When the
reaction was complete, the product was extracted with CH Cl .
2
2
All the CH Cl was evaporated under vacuo, and the product
2
2
1
016. (i) Siele, V. I. J. Heterocycl. Chem. 1997, 14, 337. (j) Daigle,
D. J.; Pepperman, A. B. Jr.; Vail, S. L. J. Heterocycl. Chem. 1974, 11,
07. (k) Daigle, D. J. Inorg. Synth. 1998, 32, 40.
ketone or aldehyde was isolated from the crude mixture by
column chromatography (silica gel, hexane–EtOAc). The forma-
tion and purity of all the products were confirmed by compar-
4
1
(
9) (a) Bravo, J.; Bolaño, S.; Gonsalvi, L.; Peruzzini, M. Coord. Chem.
Rev. 2010, 254, 555. (b) Phillips, A. D.; Gonsalvi, L.; Romerosa,
A.; Vizza, F.; Peruzzini, M. Coord. Chem. Rev. 2004, 248, 955.
ing their H NMR spectra with the report values.
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A: Chem. 1996, 108, 87. (b) Johansson, A. J.; Zuidema, E.; Bolm, C.
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©
Georg Thieme Verlag Stuttgart · New York — Synlett 2018, 29, A–E