10.1002/chem.201701630
Chemistry - A European Journal
FULL PAPER
diluted to 0.015 M, cooled to -20 or 0 °C, and the Rh2(R-PTAD)4
catalyst was added. The insertion reaction was stirred for 3-18 hours.
The solvent was then evaporated to give the crude product. Column
chromatography using 2-5% EtOAc/hexanes afforded the desired
product.
[2]
[3]
Doyle, M. P.; Brandes, B. D.; Kazala, A. P.; Pieters, R. J.; Jarstfer,
M. B.; Watkins, L. M.; Eagle, C. T. Tetrahedron Lett. 1990, 31,
6613-6616.
For comprehensive reviews on C–H insertion, see: a) Doyle, M. P.;
Duffy, R.; Ratnikov, M.; Zhou, L. Chem. Rev. 2010, 110, 704-724; b)
Davies, H. M. L.; Denton, J. R. Chem. Soc. Rev. 2009, 38, 3061-
3071; c) Santiago, J. V.; Machado, A. H. L. Beilstein J. Org. Chem.
2016, 12, 882-902.
General Procedure K for the in-situ monitoring of the C–H
insertion reaction
[4]
a) Taber, D. F.; Petty, E. H. J. Org. Chem. 1982, 47, 4808-4809; b)
Taber, D. F.; Ruckle, R. E. J. Am. Chem. Soc. 1986, 108, 7686-
7693; c) Doyle, M. P.; Van Oeveren, A.; Westrum, L. J.;
Protopopova, M. N.; Clayton, T. W. J. Am. Chem. Soc. 1991, 113,
8982-8984
A flame-dried three-necked round bottom flask and magnetic stir bar
was fitted with two rubber septa (left and right ports) and a glass
stopper (center port). Through one of the side septa a hole was
bored through which the IR probe was inserted. The resulting setup
was cooled under argon and placed into a preheated water bath set at
25 ºC. After configuring the IR acquisition parameters, acetonitrile (5
mL) was then added and the instrument was blanked. The spectral
acquisition was initiated and a baseline signal was acquired. After a
stable signal was achieved, hydrazone (.5 mmol, 0.1 M) was added
through the center port and was allowed to stir for ~20 min to allow for
thermal equilibration. MnO2 (348 mg, 4 mmol, 8 equiv.) was then
added in one portion and the resulting suspension was allowed to stir
vigorously until there was no noticeable change in the diazo signals.
For the cyclization, an additional 5 mL aliquot of acetonitrile was
added to the stirring reaction to obtain a nominal concentration of 0.5
M. The water bath was then replaced with an ice bath. After the
reaction temperature become constant (~30 min), Rh2(R-PTAD)4
(7.80 mg, 0.005 mmol, 0.01 equiv.) was added.
[5]
[6]
a) Ye, T.; McKervey, M. A. Chem. Rev. 1994, 94, 1091-1160; b)
Doyle, M. P.; Forbes, D. C. Chem. Rev. 1998, 98, 911-936.
a) Davies, H. M. L.; Hansen, T. J. Am. Chem. Soc. 1997, 119, 9075-
9076; b) Davies, H. M. L.; Denton, J. R. Chem. Soc. Rev. 2009, 38,
3061-3071; c) Davies, H. M. L.; Pelphrey, P. M. Organic Reactions
(Hoboken, NJ, United States) 2011, 75, 75-212.
[7]
[8]
a) Zhu, D.; Ma, J.; Luo, K.; Fu, H.; Zhang, L.; Zhu, S. Angew. Chem.,
Int. Ed. 2016, 55, 8452-8456; b) Ma, X.; Wu, F.; Yi, X.; Wang, H.;
Chen, W. Chem. Commun. 2015, 51, 6862-6865; c) Zhang, Y.;
Wang, D.; Cui, S. Org. Lett. 2015, 17, 2494-2497.
Examples of metal-catalyzed reactions of diaryldiazomethanes
include: a) Mehrotra, K. N.; Singh, G. S. Indian J. Chem., Sect. B:
Org. Chem. Incl. Med. Chem. 1985, 24B, 773-774. b) Werner, H.;
Schneider, M. E.; Bosch, M.; Wolf, J.; Teuben, J. H.; Meetsma, A.;
Troyanov, S. I. Chem. Eur. J. 2000, 6, 3052-3059. e) Petursson, S.
Carbohydr. Res. 2001, 331, 239-245. f) Petursson, S.; Jonsdottir, S.
Tetrahedron Asymmetry 2012, 23, 157-163; g) Qiu, L.; Huang, D.;
Xu, G.; Dai, Z.; Sun, J. Org. Lett. 2015, 17, 1810-1813; h) Zhang,
Y.; Wang, D.; Cui, S. Org. Lett. 2015, 17, 2494-2497.
Acknowledgements
KNL acknowledges support from the Department of
Education GAANN Fellowship, the Department of Chemistry
Borge Fellowship, and the UC Davis Graduate Research
Award. AJK thanks UC Davis Provost Undergraduate
Fellowship (PUF) and the Arnold and Mabel Beckman
Foundation. CS thanks CAPES (Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior) and the
Brazilian Ministry of Education for a postdoctoral fellowship.
JH gratefully acknowledge Mettler-Toledo Autochem for the
donation of an EasyMax 402 Process Reaction Platform.
Additionally, we thank Merck Research Labs for student
research fellowships (to R.C.). MCR would like to
acknowledge the Ministerio de Educación y Ciencia for the
FPU fellowship and to the Fundación Pedro Barrié de la
Maza for a fellowship to visit the Tantillo lab and professors
Carlos Silva López and Olalla Nieto Faza for helpful
comments.
[9]
a) Ma, X. J.; Wu, F. F.; Yi, X. F.; Wang, H. X.; Chen, W. Z. Chem.
Comm. 2015, 51, 6862-6865; b) Zhu, D.; Ma, J.; Luo, K.; Fu, H. G.;
Zhang, L.; Zhu, S. F. Angew. Chem. Int. Ed. 2016, 55, 8452-8456.
c) W. H. Cheung, S. L. Zheng, W. Y. Yu, G. C. Zhou, C. M. Che,
Org. Lett. 2003, 5, 2535-2538; d) X. L. Dai, T. H. Warren, J. Am.
Chem. Soc. 2004, 126, 10085-10094. e) M. P. Doyle, K. G. High, S.
M. Oon, A. K. Osborn, Tetrahedron Lett. 1989, 30, 3049-3052; f) M.
A. Garcia-Garibay, H. Dang, Org. Biomol. Chem. 2009, 7, 1106-
1114; g) Y. Li, J. S. Huang, Z. Y. Zhou, C. M. Che, X. Z. You, J. Am.
Chem. Soc. 2002, 124, 13185-13193; h) H. Werner, M. E.
Schneider, M. Bosch, J. Wolf, J. H. Teuben, A. Meetsma, S. I.
Troyanov, Chem. Eur. J. 2000, 6, 3052-3059; i) S. L. Zheng, W. Y.
Yu, M. X. Xu, C. M. Che, Tetrahedron Lett. 2003, 44, 1445-1447.
[10] Soldi, C.; Lamb, K. N.; Squitieri, R. A.; González-López, M.; Di
Maso, M. J.; Shaw, J. T. J. Am. Chem. Soc. 2014, 136, 15142-
15145.
[11] a) Werlé, C.; Goddard, R.; Fürstner, A. Angew. Chem., Int. Ed. 2015,
54, 15452-15456; b) Werlé, C.; Goddard, R.; Philipps, P.; Farès, C.;
Fürstner, A. J. Am. Chem. Soc. 2016, 138, 3797-3805
[12] Sun, X. X.; Zhang, H. H.; Li, G. H.; Meng, L.; Shi, F. Chem.
Commun. 2016, 52, 2968-2971.
[13] Resveratrol in Health and Disease; Aggarwal, B. B., Shishodia, S.,
Eds.; CRC Press, Taylor and Francis Group: Boca Raton, FL, 2006.
[14] Pezet, R.; Perret, C.; Jean-Denis, J. B.; Tabacchi, R.; Gindro, K.;
Viret, O. J. Agric. Food. Chem. 2003, 51, 5488-5492.
Keywords: keyword 1 • keyword 2 • keyword 3 • keyword 4 •
keyword 5
[15] Sato, M.; Tsuchiya, H.; Miyazaki, T.; Ohyama, M.; Tanaka, T.;
Iinuma, M. Lett. Appl. Microbiol. 1995, 21, 219-222.
[16] a) Snyder, S. A.; Breazzano, S. P.; Ross, A. G.; Lin, Y. Q.; Zografos,
A. L. J. Am. Chem. Soc. 2009, 131, 1753-1765; b) Jia, Y.; Li, T.; Yu,
C.; Jiang, B.; Yao, C. Org. Biomol. Chem. 2016, 14, 1982-1987; c)
Matsuura, B. S.; Keylor, M. H.; Li, B.; Lin, Y.; Allison, S.; Pratt, D. A.;
Stephenson, C. R. J. Angew. Chem. 2015, 127, 3825-3828.
[17] a) Jeffrey, J. L.; Sarpong, R. Org. Lett. 2009, 11, 5450-5453; b)
Klotter, F.; Studer, A. Angew. Chem., Int. Ed. 2014, 53, 2473-2476;
c) Kim, I.; Choi, J. Org. Biomol. Chem. 2009, 7, 2788-2795; d) Kim,
K.; Kim, I. Org. Lett. 2010, 12, 5314-5317.
[1]
a) Reddy, R. P.; Lee, G. H.; Davies, H. M. L. Org. Lett. 2006, 8,
3437-3440; b) Davies, H. M. L.; Bruzinski, P. R.; Lake, D. H.; Kong,
N.; Fall, M. J. J. Am. Chem. Soc. 1996, 118, 6897-6907.
This article is protected by copyright. All rights reserved.