The Journal of Organic Chemistry
Article
X (1−21 in Scheme 2) were prepared by condensation of the
corresponding aldehydes with malononitrile, ethyl α-cyanoacetate, α-
cyanoacetamide, diethyl malonate. etc. in the presence of a base,
respectively,30 and were purified by recrystallizing for two times. The
corresponding saturated neutral compounds of the polar olefins X
were obtained from the reduction of X by NaBH4 or Hantzsch ester,
and the final products were identified by 1H NMR and MS
(Supporting Information). The hydride adducts of olefins (XH−)
were prepared according to Arnett’s method.31 The anion precursor
(XH2) was dissolved in dry acetonitrile, and then a slightly excess
amount of KH was added. The mixture was stirred at room tem-
perature for about 20 min and then filtered directly into the reaction
vessel. All operations were carried out in an argon-filled glovebox.
Measurements of Redox Potentials. The electrochemical
experiments were carried out by cyclic voltammetry (CV) and
Osteryoung square-wave voltammetry (OSWV) using a BAS-100B
electrochemical apparatus in deaerated acetonitrile under an argon
atmosphere at 298 K as described previously.32 n-Bu4NPF6 (0.1 M) in
acetonitrile was employed as the supporting electrolyte. A standard
three-electrode cell consists of a glassy carbon disk as a working
electrode, a platinum wire as a counter electrode, and 0.1 M AgNO3/
Ag (in 0.1 M n-Bu4NPF6/acetonitrile) as a reference electrode. The
ferrocenium/ferrocene redox couple (Fc+/0) was taken as the internal
standard. The reproducibilities of the potentials were usually ⩽5 mV
for ionic species and ⩽10 mV for neutral species.
(2) (a) Haibach, M. C.; Kundu, S.; Brookhart, M.; Goldman, A. S.
Acc. Chem. Res. 2012, 45, 947−958. (b) Deubel, D. V.; Frenking, G.;
Gisdakis, G.; Herrmann, W. A.; Rosch, N.; Sundermeyer, J. Acc. Chem.
̈
Res. 2004, 37, 645−652. (c) Kakiuchi, F.; Murai, S. Acc. Chem. Res.
2002, 35, 826−834. (d) Mangion, D.; Arnold, D. R. Acc. Chem. Res.
2002, 35, 297−304. (e) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res.
2001, 34, 18−29. (f) Ruasse, M. F. Acc. Chem. Res. 1990, 23, 87−93.
(3) (a) Dias, H. V. R.; Lovely, C. J. Chem. Rev. 2008, 108, 3223−
3238. (b) Bartsch, R. A.; Zavada, J. Chem. Rev. 1980, 80, 453−494.
(c) Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87−99. (d) Parks, G.
S. Chem. Rev. 1936, 18, 325−334. (e) Ohlmann, D. M.; Tschauder, N.;
Stockis, J.; Gooßen, K.; Dierker, M.; Gooßen, L. J. J. Am. Chem. Soc.
2012, 134, 13716−13729. (f) Biswas, S.; Huang, Z.; Choliy, Y.; Wang,
D. Y.; Brookhart, M.; Krogh-Jespersen, K.; Goldman, A. S. J. Am.
Chem. Soc. 2012, 134, 13276−13295. (g) Amakawa, K.; Wrabetz, S.;
Krohnert, J.; Tzolova-Muller, G.; Schlogl, R.; Trunschke, A. J. Am.
̈
̈
̈
Chem. Soc. 2012, 134, 11462−11473. (h) Rupar, P. A.; Cambridge, G.;
Winnik, M. A.; Manners, I. J. Am. Chem. Soc. 2011, 133, 16947−16957.
(i) Wu, Y.; Singh, R. P.; Deng, L. J. Am. Chem. Soc. 2011, 133, 15219−
15219. (j) Wu, Y.; Singh, R. P.; Deng, L. J. Am. Chem. Soc. 2011, 133,
12458−12461. (k) Babushkin, D. E.; Brintzinger, H. H. J. Am. Chem.
Soc. 2010, 132, 452−453. (l) Ohara, K.; Kawano, M.; Inokuma, Y.;
Fujita, M. J. Am. Chem. Soc. 2010, 132, 30−31. (m) Rios, I. G.;
Novarino, E.; van der Veer, S.; Hessen, B.; Bouwkamp, M. W. J. Am.
Chem. Soc. 2009, 131, 16658−16659. (n) Meek, S. J.; Malcolmson, S.
J.; Li, B.; Schrock, R. R.; Hoveyda, A. H. J. Am. Chem. Soc. 2009, 131,
16407−16409. (o) Wolfe, J. P.; Rossi, M. A. J. Am. Chem. Soc. 2004,
126, 1620−1621. (p) Nam, W.; Park, S.; Lim, I. K.; Lim, M. H.; Hong,
J.; Kim, J. J. Am. Chem. Soc. 2003, 125, 14674−14675. (q) Takayama,
Y.; Delas, C.; Muraoka, K.; Uemura, M.; Sato, F. J. Am. Chem. Soc.
2003, 125, 14163−14167.
Isothermal Titration Calorimetry (ITC). The titration experi-
ments were performed on a CSC4200 isothermal titration calorimeter
in acetonitrile at 298 K as described previously.33 The performance of
the calorimeter was checked by measuring the standard heat of
neutralization of an aqueous solution of sodium hydroxide with a
standard aqueous HCl solution. Data points were collected every 2 s.
The heat of reaction was determined following eight automatic injec-
tions from a 250 μL injection syringe containing a standard solution
(≈2 mM) into the reaction cell (1.30 mL) containing 1 mL of another
concentrated reactant (≈15 mM). The injection volume (5 μL) was
delivered at a 0.5 s time interval with 300 s between every two
injections. The reaction heat was obtained by integration of each peak
except the first.
́
(4) (a) Robles, O.; Serna-Saldívar, S. O.; Gutierrez-Uribe, J. A.;
Romo, D. Org. Lett. 2012, 14, 1394−1397. (b) Yoshida, K.; Hayashi,
K.; Yanagisawa, A. Org. Lett. 2011, 13, 4762−4765. (c) Okamoto, R.;
Okazaki, E.; Noguchi, K.; Tanaka, K. Org. Lett. 2011, 13, 4894−4897.
(d) Matsuoka, S.; Ota, Y.; Washio, A.; Katada, A.; Ichioka, K.; Takagi,
K.; Suzuki, M. Org. Lett. 2011, 13, 3722−3725. (e) Qi, W.; Zhu, T.;
Xu, M. Org. Lett. 2011, 13, 3410−3413.
ASSOCIATED CONTENT
* Supporting Information
(5) (a) Dhara, K.; Midya, G. C.; Dash, J. J. Org. Chem. 2012, 77,
8071−8082. (b) Hyun, M. Y.; Kim, S. H.; Song, Y. J.; Lee, H. J.; Jo, Y.
D.; Kim, J. H.; Hwang, I. H.; Noh, J. Y.; Kang, J.; Kim, C. J. Org. Chem.
■
S
The correlation plots of the six thermodynamic affinities against
the Hammett parameters of the remote substituents and the
representative 1H NMR spectra of the polar olefins. This
material is available free of charge via the Internet at http://
2012, 77, 7307−7312. (c) Karimiahmadabadi, M.; Erfan, S.; Foldesi,
̈
A.; Chattopadhyaya, J. J. Org. Chem. 2012, 77, 6855−6872. (d) Xue,
F.; Wang, D.; Li, X.; Wan, B. J. Org. Chem. 2012, 77, 3071−3081.
(e) Zhang, F.; Zaidi, S.; Haney, K. M.; Kellogg, G. E.; Zhang, Y. J. Org.
Chem. 2011, 76, 7945−7952. (f) Voigtritter, K.; Ghorai, S.; Lipshutz,
B. H. J. Org. Chem. 2011, 76, 4697−4702. (g) Lesma, G.; Colombo, A.;
Sacchetti, A.; Silvani, A. J. Org. Chem. 2009, 74, 590−596. (h) Kajihara,
K.; Arisawa, M.; Shuto, S. J. Org. Chem. 2008, 73, 9494−9496.
(6) (a) Smith, A. B., III; Condon, S. M.; McCauley, J. A. Acc. Chem.
Res. 1998, 31, 35−46. (b) McReynolds, M. D.; Dougherty, J. M.;
Hanson, P. R. Chem. Rev. 2004, 104, 2239−2258. (c) Zeni, G.; Larock,
R. C. Chem. Rev. 2004, 104, 2285−2310. (d) Crimmins, M. T. Chem.
Rev. 1988, 88, 1453−1473.
AUTHOR INFORMATION
Corresponding Author
■
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
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(7) (a) Kashif, R.; Khan, M.; Zhugralin, A. R.; Torker, S.; O’Brien, R.
V.; Lombardi, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 2012, 134,
12438−12441. (b) Peryshkov, D. V.; Schrock, R. R.; Takase, M. K.;
Financial support from the National Natural Science
Foundation of China (Grant Nos. 21072104, 20921120403,
20832004, and 21102074), the Ministry of Science and
Technology of China (Grant No. 2004CB719905), and the
111 Project (B06005) is gratefully acknowledged.
Muller, P.; Hoveyda, A. H. J. Am. Chem. Soc. 2011, 133, 20754−20757.
̈
(c) Keitz, B. K.; Endo, K.; Patel, P. R.; Herbert, M. B.; Grubbs, R. H. J.
Am. Chem. Soc. 2012, 134, 693−699. (d) Snyder, S. A.; Tang, Z. Y.;
Gupta, R. J. Am. Chem. Soc. 2009, 131, 5744−5745. (e) Lu, Y. X.;
Guan, Z. J. Am. Chem. Soc. 2012, 134, 14226−14231.
REFERENCES
■
(8) (a) Ramachary, D. B.; Kishor, M.; Reddy, Y. V. Eur. J. Org. Chem.
2008, 975−993. (b) Tarnopolsky, A.; Hoz, S. J. Am. Chem. Soc. 2007,
129, 3402−3407. (c) Hong, Y.-T.; Barchuk, A.; Krische, M. J. Angew.
Chem., Int. Ed. 2006, 45, 6885−6888. (d) He, P.; Watts, P.; Marken,
F.; Haswell, S. J. Angew. Chem., Int. Ed. 2006, 45, 4146−4149. (e) Patil,
N. T.; Huo, Z.; Yamamoto, Y. J. Org. Chem. 2006, 71, 2503−2506.
(1) (a) Carey, F. A. Organic Chemistry, 5th ed.; McGraw-Hill Higher
Education: New York, 2003; pp 230−271. (b) Streitwieser, A.;
Heathcock, C. H. Introduction to Organic Chemistry, 3rd ed.; Macmillan
Publishing Company: New York, 1985; pp 232−298. (c) Solomons, T.
W. G.; Fryhle, C. B. Organic Chemistry, 8th ed.; Wiley: New York,
2004; pp 287−370.
7167
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