Angewandte
Chemie
344, 795 – 813; d) M. Beller, C. Breindl, M.
Eichberger, C. G. Hartung, J. Seayad, O. R.
Thiel, A. Tillack, H. Trauthwein, Synlett
2002, 1579 – 1594; e) F. Pohlki, S. Doye,
Chem. Soc. Rev. 2003, 32, 104 – 114; f) I.
Bytschkov, S. Doye, Eur. J. Org. Chem. 2003,
935 – 946; g) P. W. Roesky, T. E. Müller,
Angew. Chem. 2003, 115, 2812 – 2814;
Angew. Chem. Int. Ed. 2003, 42, 2708 – 2710.
[2] a) M. R. GagnØ, C. L. Stern, T. J. Marks, J.
Am. Chem. Soc. 1992, 114, 275 – 294;
b) Y. K. Kim, T. Livinghouse, J. E. Bercaw,
Tetrahedron Lett. 2001, 42, 2933 – 2935;
c) Y. K. Kim, T. Livinghouse, Angew.
Chem. 2002, 114, 3797 – 3799; Angew.
Chem. Int. Ed. 2002, 41, 3645 – 3647; d) J.-
S. Ryu, G. Y. Li, T. J. Marks, J. Am. Chem.
Soc. 2003, 125, 12584 – 12605; e) S. Hong, S.
Tian, M. V. Metz, T. J. Marks, J. Am. Chem.
Soc. 2003, 125, 14768 – 14783; f) S. Hong,
A. M. Kawaoka, T. J. Marks, J. Am. Chem.
Soc. 2003, 125, 15878 – 15892; g) P. N. OꢀSh-
aughnessy, P. D. Knight, C. Morton, K. M.
Gillespie, P. Scott, Chem. Commun. 2003,
1770 – 1771; h) J.-S. Ryu, T. J. Marks, F. E.
McDonald, J. Org. Chem. 2004, 69, 1038 –
1052; i) D. V. Gribkov, K. C. Hultzsch,
Scheme 3. Proposed mechanism for zirconÀocene-catalyzed hydroamination/cyclization of
aminoalkenes. XÀ =CH3B(C6F5)3À, B(C6F5)4
.
Chem. Commun. 2004, 730 – 731; j) K. C.
Hultzsch, F. Hampel, T. Wagner, Organo-
metallics 2004, 23, 2601 – 2612.
Experimental Section
All operations were performed under an inert atmosphere of nitrogen
or argon using standard Schlenk-line or glove-box techniques.
Metallocene dichlorides (Fluka), B(C6F5)3 (Strem), and
[PhNMe2H]+[B(C6F5)4]À (Strem) were used as received.
[3] General reviews on the application of Group 4 complexes in
organic synthesis: a) Titanium and Zirconium in Organic Syn-
thesis (Ed.: I. Marek), Wiley-VCH, Weinheim, 2002; b) A. H.
Hoveyda, J. P. Morken, Angew. Chem. 1996, 108, 1378 – 1401;
Angew. Chem. Int. Ed. Engl. 1996, 35, 1262 – 1284.
[4] For some recent examples see: a) I. Bytschkov, S. Doye,
Tetrahedron Lett. 2002, 43, 3715 – 3718; b) L. Ackermann,
R. G. Bergman, Org. Lett. 2002, 4, 1475 – 1478; c) Y. Shi, C.
Hall, J. T. Ciszewski, C. Cao, A. L. Odom, Chem. Commun.
2003, 586 – 587; d) C. Li, R. K. Thomson, B. Gillon, B. O. Patrick,
L. L. Schafer, Chem. Commun. 2003, 2462 – 2463; e) L. Acker-
mann, Organometallics 2003, 22, 4367 – 4368; f) Z. Zhang, L. L.
Schafer, Org. Lett. 2003, 5, 4733 – 4736; g) V. Khedkar, A.
Tillack, M. Beller, Org. Lett. 2003, 5, 4767 – 4770; h) H.
Siebeneicher, I. Bytschkov, S. Doye, Angew. Chem. 2003, 115,
3151 – 3153; Angew. Chem. Int. Ed. 2003, 42, 3042 – 3044; i) I.
Bytschkov, H. Siebeneicher, S. Doye, Eur. J. Org. Chem. 2003,
2888 – 2902; j) F. Pohlki, I. Bytschkov, H. Siebeneicher, A.
Heutling, W. A. König, S. Doye, Eur. J. Org. Chem. 2004,
1967 – 1972; k) C. Lorber, R. Choukroun, L. Vendler, Organo-
metallics 2004, 23, 1845 – 1850.
[Cp2ZrMe2],[17]
[Cp2 ZrMe2],
[Cp2Ti(CH2Ph)2],[19]
and
[18]
*
[Cp2ZrMe]+[MeB(C6F5)3]À (1a),[9] were synthesized as described in
the literature. The substrates were dried by distillation from CaH2 and
stored over molecular sieves.
Representative procedure: 5·HCl (Table 2, entry 4): In the glove
box, a flask was fitted with a stirring bar and was charged with 1a
(8.0 mg, 10.5 mmol) toluene (0.5 mL) and 4 (108 mg, 1.09 mmol). The
solution was heated to 1008C for 17 h. All volatiles were then
vacuum-transferred, diluted with diethyl ether (2 mL), and treated
with hydrochloric acid (1.2 mL, 1m in Et2O, 1.2 mmol) at 08C. After
30 min, the suspension was brought to room temperature and the
solvent removed in vacuo. The white precipitate was washed with
diethyl ether and then dried in air to give 124 mg (84%) of a white
1
powder. H NMR (300 MHz, D2O, 25 8C): d = 3.70 (m, 1H, CH2N),
3.41 (m, 1H, NCHCH3), 3.17 (m, 1H, CH2N), 2.91 (s, 3H, CH3), 2.36
(m, 1H, NCH(CH3)CH2), 2.03–2.16 (m, 2H, NCH2CH2), 1.75 (m, 1H,
NCH(CH3)CH2), 1.43 ppm (d, 3J(H,H) = 6.5 Hz, 3H, CHCH3);
13C{1H} NMR (75.5 MHz, D2O, 25 8C, SiMe4): d = 66.2 (NCHCH3),
56.7 (CH2N), 39.2 (NCH3), 31.7 (NCH(CH3)CH2), 21.5 (NCH2CH2),
15.7 ppm (CHCH3).
[5] P. L. Watson, G. W. Parshall, Acc. Chem. Res. 1985, 18, 51 – 56.
[6] a) H. H. Brintzinger, D. Fischer, R. Mühlhaupt, B. Rieger, R.
Waymouth, Angew. Chem. 1995, 107, 1255 – 1283; Angew. Chem.
Int. Ed. Engl. 1995, 34, 1143 – 1170; b) E. Y.-X. Chen, T. J.
Marks, Chem. Rev. 2000, 100, 1391 – 1434.
Substrates 6, 8, and 10 were cyclized by similar procedures.
Received: June 4, 2004
[7] a) R. B. Grossman, W. M. Davis, S. L. Buchwald, J. Am. Chem.
Soc. 1991, 113, 2321 – 2322; b) G. A. Molander, C. P. Corrette,
Tedrahedron Lett. 1998, 39, 5011 – 5014; c) K. H. Shaughnessy,
R. M. Waymouth, Organometallics 1998, 17, 5728 – 5745;
d) M. V. Troutman, D. H. Appella, S. L. Buchwald, J. Am.
Chem. Soc. 1999, 121, 4916 – 4917; e) A. D. Sadow, T. D. Tilley,
Organometallics 2003, 22, 3577 – 3585.
[8] a) P. D. Knight, I. Munslow, P. N. OꢀShaughnessy, P. Scott,Chem.
Commun. 2004, 894 – 895; b) A report describing a cationic
alkylscandium-based hydroamination catalyst system appeared
Keywords: homogeneous catalysis · hydroamination ·
metallocenes · titanium · zirconium
.
[1] a) T. E. Müller, M. Beller, Chem. Rev. 1998, 98, 675 – 703; b) M.
Nobis, B. Drießen-Hölscher, Angew. Chem. 2001, 113, 4105 –
4108; Angew. Chem. Int. Ed. 2001, 40, 3983 – 3985; c) J. Seayad,
A. Tillack, C. G. Hartung, M. Beller, Adv. Synth. Catal. 2002,
Angew. Chem. Int. Ed. 2004, 43, 5542 –5546
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