LETTER
Hydrations and Hydroaminations of (Dicyclopropylmethylene)cyclopropane
1517
Rodriguez-Zubiri, M. Eur. J. Org. Chem. 2007, 4711.
(12) (a) Huang, X.; Fu, W.-J. Synthesis 2006, 1016. (b) Shao,
L.-X.; Xu, B.; Huang, J.-W.; Shi, M. Chem. Eur. J. 2006, 12,
510. (c) Siriwardana, A. I.; Kathriarachchi, K. K. A. D. S.;
Nakamura, I.; Yamamoto, Y. Heterocycles 2005, 66, 333.
(d) Chen, Y.; Shi, M. J. Org. Chem. 2004, 69, 426. (e) Shi,
M.; Xu, B.; Huang, J.-W. Org. Lett. 2004, 6, 1175. (f) Shi,
M.; Chen, Y.; Xu, B.; Tang, J. Green Chem. 2003, 5, 85.
(g) Shi, M.; Chen, Y.; Xu, B.; Tang, J. Tetrahedron Lett.
2002, 43, 8019.
(13) Danishefsky, S. Acc. Chem. Res. 1979, 12, 66.
(14) For rare notable exceptions, see: (a) Fua, W.; Xian Huang,
X. Tetrahedron Lett. 2008, 49, 562. (b) Li, Q.; Shi, M.;
Timmons, C.; Li, G. Org. Lett. 2006, 8, 625.
(d) Hultzsch, K. C. Adv. Synth. Catal. 2005, 347, 367.
(e) Alonso, F.; Beletskaya, I. P.; Yus, M. Chem. Rev. 2004,
104, 3079. (f) Hultzsch, K. C.; Hampel, F.; Wagner, T.
Organometallics 2004, 23, 2601. (g) Roesky, P. W.; Müller,
T. E. Angew. Chem. Int. Ed. 2003, 42, 2708. (h) Müller,
T. E.; Beller, M. Chem. Rev. 1998, 98, 675.
(3) For selected recent examples, see: (a) Reznichenko, A. L.;
Nguyen, H. N.; Hultzsch, K. C. Angew. Chem. Int. Ed. 2010,
49, 8984. (b) Julian, L. D.; Hartwig, J. F. J. Am. Chem. Soc.
2010, 132, 13813. (c) Leitch, D. C.; Turner, C. S.; Schafer,
L. L. Angew. Chem. Int. Ed. 2010, 49, 6382. (d) Behr, A.;
Johnen, L.; Rentmeister, N. Adv. Synth. Catal. 2010, 352,
2062. (e) Shen, X. Q.; Buchwald, S. L. Angew. Chem. Int.
Ed. 2010, 49, 564. (f) Toups, K. L.; Widenhoefer, R. A.
Chem. Commun. 2010, 46, 1712; and references cited
therein.
(15) Kozhushkov, S. I.; Yufit, D. S.; Ackermann, L. Org. Lett.
2008, 10, 3409.
(16) For selected reports on ruthenium-catalyzed C–H bond
functionalizations from our laboratories, see:
(4) For selected recent examples, see: (a) Shapiro, N. D.;
Rauniyar, V.; Hamilton, G. L.; Wu, J.; Toste, F. D. Nature
(London) 2011, 470, 245. (b) Qureshi, Z. S.; Deshmukh,
K. M.; Tambade, P. J.; Dhake, K. P.; Bhalchandra, M.;
Bhanage, B. M. Eur. J. Org. Chem. 2010, 6233. (c) Taylor,
J. G.; Adrio, L. A.; Hii, K. K. Dalton Trans. 2010, 39, 1171.
(d) Ackermann, L.; Althammer, A. Synlett 2008, 995.
(e) Cheng, X. J.; Xia, Y. Z.; Wei, H.; Xu, B.; Zhang, C.; Li,
Y.; Qian, G.; Zhang, X.; Li, K.; Li, W. Eur. J. Org. Chem.
2008, 1929. (f) Ackermann, L.; Kaspar, L. T.; Althammer,
A. Org. Biomol. Chem. 2007, 5, 1975; and references cited
therein.
(5) For representative reviews, see: (a) Masarwa, A.; Marek, I.
Chem. Eur. J. 2010, 16, 9712. (b) Pellissier, H. Tetrahedron
2010, 66, 8341. (c) Audran, G.; Pellissier, H. Adv. Synth.
Catal. 2010, 352, 575. (d) de Meijere, A.; Kozhushkov,
S. I.; Schill, H. Chem. Rev. 2006, 106, 4926. (e) Brandi, A.;
Cicchi, S.; Cordero, F. M.; Goti, A. Chem. Rev. 2003, 103,
1213. (f) Brandi, A.; Goti, A. Chem. Rev. 1998, 98, 589.
(6) For selected reviews on metal-catalyzed reactions of MCPs,
see: (a) Rubin, M.; Rubina, V.; Gevorgyan, V. Chem. Rev.
2007, 107, 3117. (b) Nakamura, I.; Yamamoto, Y. Adv.
Synth. Catal. 2002, 344, 111. (c) Binger, P.; Schmidt, T. In
Methods of Organic Chemistry (Houben-Weyl), Vol. E17c;
de Meijere, A., Ed.; Thieme: Stuttgart, 1997, 2217–2294.
(d) Lautens, M.; Klute, W.; Tam, W. Chem. Rev. 1996, 96,
49. (e) Binger, P.; Büch, H. M. Top. Curr. Chem. 1987, 135,
77.
(a) Ackermann, L.; Vicente, R.; Potukuchi, H. K.; Pirovano,
V. Org. Lett. 2010, 12, 5032. (b) Ackermann, L.; Novák, P.;
Vicente, R.; Pirovano, V.; Potukuchi, H. K. Synthesis 2010,
2245. (c) Ackermann, L.; Novák, P. Org. Lett. 2009, 11,
4966. (d) Ackermann, L.; Born, R.; Vicente, R.
ChemSusChem 2009, 546. (e) Ackermann, L.; Vicente, R.;
Althammer, A. Org. Lett. 2008, 10, 2299. (f) Ackermann,
L.; Althammer, A.; Born, R. Tetrahedron 2008, 64, 6115.
(g) Ackermann, L.; Althammer, A.; Born, R. Synlett 2007,
2833. (h) Review: Ackermann, L.; Vicente, R. Top. Curr.
Chem. 2010, 292, 211. (i) Ruthenium-catalyzed
hydroamination: Ackermann, L.; Althammer, A. Synlett
2006, 3125.
(17) (a) 1H NMR and 13C NMR spectra of 2 were identical to
those of an independently prepared sample, following a
published procedure. See: Hanack, M.; Eggensperger, H.
Liebigs Ann. Chem. 1963, 663, 31. (b) Compound 2: 1H
NMR (250 MHz, CDCl3): d = 1.61 (s, 1 H), 0.79–0.90 (m, 3
H), 0.43–0.49 (m, 6 H), 0.29–0.40 (m, 6 H). 13C NMR (62.9
MHz, CDCl3): d = 69.7 (C), 18.7 (CH), –0.1 (CH2). [D]1-2:
1H NMR (250 MHz, CDCl3): d = 1.60 (s, 1 H), 0.79–0.91 (m,
2 H), 0.43–0.49 (m, 6 H), 0.28–0.40 (m, 6 H). 13C NMR
(62.9 MHz, CDCl3): d = 69.7 (C), 18.7 (CD), 18.3 (t, J = 24.0
Hz, CH), –0.1 (CH2), –0.2 (CH2).
(18) The use of pure HCl as the catalyst may result in ring-
opening reactions even under mild reaction conditions:
Donskaya, N. A.; Shulishov, E. V.; Shabarov, Y. S. Zh. Org.
Khim. 1981, 17, 2102.
(7) (a) Siriwardana, A. I.; Kamada, M.; Nakamura, I.;
Yamamoto, Y. J. Org. Chem. 2005, 70, 5932.
(19) However, traces (<5%) of a ring-opened product were
detected in the 1H NMR spectrum of crude product 7b.
(20) General Procedure for the Preparation of
Benzyl(tricyclopropylmethyl)amine (7a),
(b) Nakamura, I.; Itagaki, H.; Yamamoto, Y. Chem.
Heterocycl. Compd. (Engl. Transl.) 2001, 37, 1532.
(c) Nakamura, I.; Itagaki, H.; Yamamoto, Y. J. Org. Chem.
1998, 63, 6458.
Phenethyl(tricyclopropylmethyl)amine (7b) and
n-Octyl(tricyclopropylmethyl)amine (7c): A flame-dried
Schlenk flask was cooled and charged with 1, (402.6 mg,
442.1 mL, 3.0 mmol), the corresponding amine (1.0 equiv)
and NH4Cl (16.0 mg, 10 mol%) in anhyd 1,4-dioxane (3.0
mL) under Ar. After stirring the reaction mixture for 48 h at
120 °C, Et2O (50 mL) was added at ambient temperature,
and the reaction mixture was extracted with aq HCl (0.1 N,
2 × 80 mL). The combined aqueous phases were washed
with Et2O (2 × 50 mL) and, after addition of aq NaOH (1 N,
25 mL), extracted with CH2Cl2 (3 × 40 mL). The combined
organic phases were dried over K2CO3 and concentrated
under reduced pressure. The residue was dissolved in MeOH
(20 mL), stirred with charcoal (2.0 g) at ambient temperature
overnight, quickly filtered through a thin pad of silica gel
and concentrated in vacuo. Amines 7a–c (1.0 mmol) were
dissolved in CH2Cl2 (5.0 mL), and a solution of p-TsOH·H2O
(190.2 mg, 1.0 mmol, 1.0 equiv) in MeOH (2.0 mL) was
(8) Shi, M.; Liu, L. P.; Tang, J. Org. Lett. 2006, 8, 4043.
(9) (a) Smolensky, E.; Kapon, M.; Eisen, M. S. Organometallics
2007, 26, 4510. (b) Smolensky, E.; Kapon, M.; Eisen, M. S.
Organometallics 2005, 24, 5495.
(10) Ryu, J.-S.; Li, G. Y.; Marks, T. J. J. Am. Chem. Soc. 2003,
125, 12584.
(11) (a) Scott, M. E.; Lautens, M. J. Org. Chem. 2008, 73, 8154.
(b) Scott, M. E.; Bethuel, Y.; Lautens, M. J. Am. Chem. Soc.
2007, 129, 1482. (c) Taillier, C.; Lautens, M. Org. Lett.
2007, 9, 591. (d) Scott, M. E.; Schwarz, C. A.; Lautens, M.
Org. Lett. 2006, 8, 5521. (e) Lu, L.; Chen, G.; Ma, S. Org.
Lett. 2006, 8, 835. (f) Scott, M. E.; Lautens, M. Org. Lett.
2005, 7, 3045. (g) Scott, M. E.; Han, W.; Lautens, M. Org.
Lett. 2004, 6, 3309.
Synlett 2011, No. 11, 1515–1518 © Thieme Stuttgart · New York