N. Nishina, Y. Yamamoto / Tetrahedron 65 (2009) 1799–1808
1807
J¼16.0, 5.6 Hz), 6.57 (1H, d, J¼16.0 Hz), 6.65 (1H, s), 6.66–6.68(1H,
References and notes
m), 6.73 (1H, t, J¼7.3 Hz), 6.94–7.02 (2H, m), 7.15–7.21 (2H, m), 7.31
(2H, dd, J¼7.7, 5.6 Hz); 13C NMR (125 MHz, CDCl3)
d 46.2, 113.1, 115.5
1. For selected recent reviews on gold catalysis, see: (a) Hashmi, A. S. K.; Hutch-
ings, G. J. Angew. Chem., Int. Ed. 2006, 45, 7896; (b) Gorin, D. J.; Toste, F. D. Nature
2007, 446, 395; (c) Hashmi, A. S. K. Chem. Rev. 2007, 107, 3180; (d) Fu¨rstner, A.;
Davies, P. W. Angew. Chem., Int. Ed. 2007, 46, 3410; (e) Patil, N. T.; Yamamoto, Y.
ARKIVOC 2007, v, 6; (f) Patil, N. T.; Yamamoto, Y. ARKIVOC 2007, x, 121; (g)
Yamamoto, Y., Lipshutz, B., Eds. Chem. Rev. 2008, 108, 2793; (h) Muzart, J. Tet-
rahedron 2008, 64, 5815; (i) Widenhoefer, R. A. Chem.dEur. J. 2008, 14, 5382; (j)
Arcadi, A. Chem. Rev. 2008, 108, 3266; (k) Gorin, D. J.; Sherry, B. D.; Toste, F. D.
Chem. Rev. 2008, 108, 3351.
[d, J (13C–19F)¼21.7 Hz], 117.8, 126.8 [d, J (13C–19F)¼2.8 Hz], 127.8 [d,
J (13C–19F)¼7.6 Hz], 129.3, 130.4, 133.0 [d, J (13C–19F)¼1.9 Hz], 147.9,
162.3 [d, J (13C–19F)¼246.6 Hz]; IR (neat) 3413, 3050, 2834, 1601,
1503, 1224, 1157, 966, 844 cmꢁ1. HRMS (ESI) calcd for C15H14FN
(MþH) 228.1183, found 228.1182.
2. For recent reviews and reports of transition metal catalyzed hydro-
functionalization, see: (a) Catalytic Heterofunctionalization; Togni, A., Gru¨ tz-
macher, H., Eds.; Wiley-VCH: Weinheim, 2001; (b) Alonso, F.; Beletskaya, I. P.;
Yus, M. Chem. Rev. 2004, 104, 3079; (c) Beller, M.; Sayad, J.; Tillack, A.; Jiao, H.
Angew. Chem., Int. Ed. 2004, 43, 3368; (d) Zhang, Z. B.; Liu, C.; Kinder, R. E.; Han,
X. Q.; Qian, H.; Widenhoefer, R. A. J. Am. Chem. Soc. 2006, 128, 9066; (e)
Rosenfeld, D. C.; Shekhar, S.; Takeymiya, A.; Utsunomiya, M.; Hartwig, J. F. Org.
Lett. 2006, 8, 4179; (f) Paril, N. T.; Lutete, L. M.; Wu, H. Y.; Nirmal, K. P.; Gridnev,
I. D.; Yamamoto, Y. J. Org. Chem. 2006, 71, 4270; (g) Liu, C.; Bender, C. F.; Han, X.;
4.11.3. (E)-(3-(4-Methoxyphenyl)allyl)morpholine (5c)
Pale yellow oil; 1H NMR (500 MHz, CDCl3)
d 2.48 (4H, br s), 3.11
(2H, d, J¼6.8 Hz), 3.72 (4H, dd, J¼4.7, 4.7 Hz), 3.79 (3H, s), 6.09 (1H,
dt, J¼15.8, 6.8 Hz), 6.45 (1H, d, J¼15.8 Hz), 6.81–6.85 (2H, m), 7.27–
7.31 (2H, m); 13C NMR (125 MHz, CDCl3)
d 53.7, 55.3, 61.6, 67.0,
114.0, 123.7, 127.5, 129.6, 132.8, 159.2; IR (neat) 1605, 1509, 1242,
1173, 1113, 1027, 972, 870, 813 cmꢁ1
.
HRMS (ESI) calcd for
´
´ ˜
Widenhoefer, R. A. Chem. Commun. 2007, 3607; (h) Jimenez-Nunez, E.; Echa-
varren, A. M. Chem. Commun. 2007, 333; (i) Shen, H. C. Tetrahedron 2008, 64,
3885; (j) Krause, N.; Belting, V.; Deutsch, C.; Erdsack, J.; Fan, H.-T.; Gockel, B.;
Hoffmann-Ro¨der, A.; Morita, N.; Volz, F. Pure Appl. Chem. 2008, 80, 1063.
3. (a) Hashmi, A. S. K. Angew. Chem., Int. Ed. 2000, 39, 3590; (b) Hashmi, A. S. K. In
Organic Synthesis Highlights V; Schmalz, H.-G., Wirth, T., Eds.; Wiley-VCH:
Weinheim, 2003; p 56.
C14H19NO2 (MþH) 234.1489, found 234.1490.
4.11.4. (E)-(3-(4-Fluorophenyl)allyl)morpholine (5e)
Pale yellow oil; 1H NMR (500 MHz, CDCl3)
d 2.48 (4H, br s), 3.12
(2H, dd, J¼6.8, 1.1 Hz), 3.72 (4H, dd, J¼4.7, 4.7 Hz), 6.15 (1H, dt,
4. For a recent critical review on gold catalysis, which pointed out that proton is
a real catalyst in some reactions, see: Hashmi, A. S. K. Catal. Today 2007, 122, 211.
5. For recent reviews of transition metal catalyzed hydroamination, see: (a)
Widenhoefer, R. A.; Han, X. Eur. J. Org. Chem. 2006, 4555; (b) Brunet, J. J.; Chu,
N.-C.; Rodriguez-Zubiri, M. Eur. J. Inorg. Chem. 2007, 4711; (c) Yu, X. H.; Marks,
T. J. Organometallics 2007, 26, 365; (d) Tobisch, S. Chem.dEur. J 2007, 13, 4884;
(e) Stubbert, B. D.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 4253; (f) Stubbert,
B. D.; Marks, T. J. J. Am. Chem. Soc. 2007, 129, 6149; (g) Smolensky, E.; Kapon, M.;
Eisen, M. S. Organometallics 2007, 26, 4510; (h) Severin, R.; Doye, S. Chem. Soc.
Rev. 2007, 36, 1407; (i) Minatti, A.; Muniz, K. Chem. Soc. Rev. 2007, 36, 1142; (j)
Chianese, A. R.; Lee, S. J.; Gagne, M. R. Angew. Chem., Int. Ed. 2007, 46, 4042; (k)
Buil, M. L.; Esteruelas, M. A.; Lopez, A. M.; Mateo, A. C.; Onate, E. Organome-
tallics 2007, 26, 554; (l) Mueller, T. E.; Hultzsch, K. C.; Yus, M.; Foubelo, F.; Tada,
M. Chem. Rev. 2008, 108, 3795.
6. See, Ref. 2a. For other thermochemical reviews, see: (a) Roundhill, D. M. Chem.
Rev. (Washington, DC) 1992, 92, 1; (b) Steinborn, D.; Taube, R. Z. Chem. 1986, 26,
349; (c) Benson, S. W. Thermochemical Kinetics: Methods for the Estimation of
Thermochemical Data and Rate Parameters, 2nd ed.; John Wiley and Sons: New
York, NY, 1976; (d) Pedley, J. B.; Naylor, R. D.; Kirby, S. P. Thermochemical Data
and Structures of Organic Compounds, 2nd ed.; Thermodynamics Research
Center: College Station, Texas, TX, 1994; (e) Koch, H. F.; Girard; Roundhill, D. M.
Polyhedron 1999, 18, 2275; (f) Taube, R. In Applied Homogeneous Catalysis with
Organometallic Compounds, 2nd ed.; Cornils, B., Herrmann, W. A., Eds.; Wiley-
VCH: Weinheim, 1996; Vol. 1, pp 513–524.
J¼15.8, 6.8 Hz), 6.47 (1H, d, J¼15.8 Hz), 6.95–7.01 (2H, m), 7.28–7.34
(2H, m); 13C NMR (125 MHz, CDCl3)
d 53.7, 61.4, 67.0, 115.5 [d, J
(
13C–19F)¼21.7 Hz], 125.8, 127.8 [d, J (13C–19F)¼8.5 Hz], 132.2, 133.0
[d, J (13C–19F)¼3.8 Hz], 162.3 [d, J (13C–19F)¼246.6 Hz]; IR (neat)
1601, 1508, 1454, 1225, 1115, 1006, 968, 870, 846, 818 cmꢁ1. HRMS
(ESI) calcd for C13H16FNO (MþH) 222.1289, found 222.1289.
4.11.5. (E)-N-(Tridec-7-en-6-yl)morpholine (5l)
Pale yellow oil; 1H NMR (500 MHz, CDCl3)
d 0.81–0.89 (6H, m),
1.13–1.40 (14H, m), 1.95–2.06 (2H, m), 2.35–2.46 (2H, m), 2.47–2.56
(2H, m), 2.59 (1H, td, J¼9.0, 4.3 Hz), 3.62–3.72 (4H, m), 5.21 (1H, ddt,
J¼15.4, 9.0, 1.3 Hz), 5.45 (1H, dt, J¼15.4, 6.8 Hz); 13C NMR (125 MHz,
CDCl3)
d 14.0, 22.5, 22.6, 26.0, 29.1, 31.4, 31.8, 32.4, 50.4, 67.3, 68.2,
129.1,134.4; IR (neat): 2954, 2925, 2853,1453,1119, 974 cmꢁ1. HRMS
(ESI) calcd for C17H33NO (MþH) 268.2635, found: 268.2634.
4.11.6. ClAuPPh2(6-tert-Bu-2-pyridyl) (6k)
Colorless crystal; mp 151 ꢀC; 1H NMR (600 MHz, CDCl3)
d
1.25
(9H, s), 7.37–7.50 (7H, m), 7.66–7.73 (5H, m), 7.89 (1H, dd, J¼7.8,
7. For recent reviews of early transition metal catalyzed hydroamination, see: (a)
Bytschkov, I.; Doye, S. Eur. J. Org. Chem. 2003, 935; (b) Hazari, N.; Mountford, P.
Acc. Chem. Res. 2005, 38, 839.
7.8 Hz); 13C NMR (149.4 MHz, CDCl3)
d 29.9, 38.0, 120.9, 128.2, 128.7
[d, J (13C–31P)¼12.2 Hz], 129.0 [d, J (13C–31P)¼18.6 Hz], 131.7 [d, J
´
8. (a) Besson, L.; Gore, J.; Cazes, B. Tetrahedron Lett. 1995, 36, 3853; (b) Al-Masum,
(
(
13C–31P)¼2.2 Hz], 134.6 [d, J (13C–31P)¼13.6 Hz], 136.7, 151.9 [d, J
M.; Meguro, M.; Yamamoto, Y. Tetrahedron Lett. 1997, 38, 6071.
9. (a) Nishina, N.; Yamamoto, Y. Angew. Chem., Int. Ed. 2006, 45, 3314; (b) Nishina,
N.; Yamamoto, Y. Synlett 2007, 1767; For very recent examples, see: (c) Kinder,
R. E.; Zhang, Z.; Widenhoefer, R. A. Org. Lett. 2008, 10, 3157; (d) Lavallo, V.; Frey,
G. D.; Donnadieu, B.; Soleilhavoup, M.; Bertrand, G. Angew. Chem., Int. Ed. 2008,
47, 5224.
10. Recently, we found that the use of olefin enhanced the reaction rate in the
platinum-catalyzed intramolecular carboalkoxylation of alkynes; see: Naka-
mura, I.; Bajracharya, G. B.; Wu, H.; Oishi, K.; Mizushima, Y.; Gridnev, I. D.;
Yamamoto, Y. J. Am. Chem. Soc. 2004, 126, 15423.
13C–31P)¼86.0 Hz], 170.9 [d,
J
(
13C–31P)¼14.3 Hz; 31P NMR
(121.5 MHz, CDCl3)
d 31.5; IR (neat, ATR): 2957, 1578, 1474, 1435,
1173, 1140, 1102, 985, 812 cmꢁ1. Anal. Calcd for C21H22AuClP
(2ꢂcomplexþ1ꢂtoluene): C, 49.22; H, 4.38; N, 2.34; Cl, 5.93.
Found: C, 49.02; H, 4.54; N, 2.34; Cl, 6.02. HRMS (ESI) calcd for
C21H22AuClP (MþNa) 574.0736, found 574.0734.
11. For other examples of gold-mediated racemization of allenes, see: (a) Sherry,
B. D.; Toste, F. D. J. Am. Chem. Soc. 2004, 126, 15978; (b) Zhang, Z.; Bender, C. F.;
Widenhoefer, R. A. J. Am. Chem. Soc. 2007, 129, 14148; (c) Hamilton, G. L.; Kang,
E. J.; Mba, M.; Toste, F. D. Science 2007, 317, 496.
12. (a) Lersch, M.; Tilset, M. Chem. Rev. 2005, 105, 2471; (b) Feducia, J. A.; Campbell,
A. N.; Anthis, J. W.; Gagne´, M. R. Organometallics 2006, 25, 3114; (c) Romeo, R.;
D’Amico, G. Organometallics 2006, 25, 3435.
13. For examples of intramolecular gold-catalyzed hydroamination with aliphatic
amine bearing substrates, see: (a) Fukuda, Y.; Utimoto, K.; Nozaki, H. Hetero-
cycles 1987, 25, 297; (b) Fukuda, Y.; Utimoto, K. Synthesis 1991, 975; (c) Mu¨ller,
T. E.; Grosche, M.; Herdtweck, E.; Pleier, A.-K.; Walter, E.; Yan, Y.-K. Organo-
metallics 2000, 19, 170; (d) Arcadi, A.; Giuseppe, S. D.; Marinelli, F.; Rossi, E. Adv.
Synth. Catal. 2001, 343, 443; (e) Arcadi, A.; Giuseppe, S. D.; Marinelli, F.; Rossi, E.
Tetrahedron: Asymmetry 2001, 12, 2715; (f) Kadzimirsz, D.; Hildebrandt, D.;
Merz, K.; Dyker, G. Chem. Commun. 2006, 661; (g) Krause, N.; Morita, N. Org.
Lett. 2004, 6, 4121; (h) Morita, N.; Krause, N. Eur. J. Org. Chem. 2006, 4634; (i)
Aillaud, I.; Collin, J.; Hannedouche, J.; Schulz, E. Dalton Trans. 2007, 5105; See
also: (j) Bender, C. F.; Widenhoefer, R. A. Chem. Commun. 2008, 2741.
14. (a) Li, Y.; Marks, T. J. Organometallics 1996, 15, 3770; (b) Haskel, A.; Straub, T.;
Eisen, M. S. Organometallics 1996, 15, 3773; (c) Straub, T.; Haskel, A.; Neyroud,
T. G.; Kapon, M.; Botoshansky, M.; Eisen, M. S. Organometallics 2001, 20, 5017.
4.11.7. (E)-(1-(4-Phenylbut-3-en-2-yloxy)ethyl)benzene
(10-major)
Colorless oil; 1H NMR (500 MHz, CDCl3)
d
1.29 (3H, d, J¼6.6 Hz),
1.42 (3H, d, J¼6.6 Hz), 3.85 (1H, dq, J¼7.8, 6.6 Hz), 4.57 (1H, q,
J¼6.6 Hz), 6.12 (1H, dd, J¼15.8, 7.8 Hz), 6.38 (1H, d, J¼15.8 Hz), 7.20–
7.42 (10H, m); 13C NMR (125 MHz, CDCl3)
d 22.2, 24.8, 73.3, 74.3,
126.2, 126.4, 127.3, 127.6, 128.4, 128.6, 131.2, 131.8, 136.7, 144.3.
4.11.8. (E)-(1-(4-Phenylbut-3-en-2-yloxy)ethyl)benzene
(10-minor)
Colorless oil; 1H NMR (500 MHz, CDCl3)
d 1.30 (3H, d,
J¼6.4 Hz), 1.41 (3H, d, J¼6.4 Hz), 4.06 (1H, dq, J¼6.8, 6.4 Hz), 4.57
(1H, q, J¼6.4 Hz), 6.04 (1H, dd, J¼15.8, 6.8 Hz), 6.40 (1H, d,
J¼15.8 Hz), 7.13–7.37 (10H, m); 13C NMR (125 MHz, CDCl3)
d 20.9,
23.6, 73.5, 74.7, 126.2, 126.4, 127.2, 127.4, 128.3, 128.4, 129.9,
132.5, 136.9, 144.6.