V. V. Dunina et al. / Tetrahedron: Asymmetry 9 (1998) 1917–1921
1921
3. Leung, P.-H., McLaughlin, G. M., Martin, J. W. L., Wild, S. B., Inorg. Chem., 1986, 25, 3392; Dai, L., Zhou, Zh., Zhang,
Y., Ni, Ch., Zhang, Zh., Zhou, Y., J. Chem. Soc., Chem. Commun., 1987, 1760–1762; Wang, X. Ch., Cui, Y. X., Mak, Th.
C. W., Wong, H. C., J. Chem. Soc., Chem. Commun., 1990, 167–169; Chelucci, G., Cabras, M. A., Saba, A., Sechi, A.,
Tetrahedron: Asymmetry, 1996, 7, 1027–1032.
20
4. For (SCRN,SS)-2a: m.p. (dec) 204–206°C, [α]D −34.3 (c 1.5, MeOH). Anal. calcd: C, 56.18; H, 6.41; N, 7.86 for
1
C25H32ClN3Pd·H2O. Found: C, 56.01; H, 6.14; N, 7.75. Diastereomeric purity (88% de) was determined by H NMR
using the integral intensity of the Me groups of the NPri substituent.
1
5. The H NMR spectra of the starting mixture of dimer (SCRN)-1 and racemic Stien in a 1:4 molar ratio contains two
sets of signals from the two diastereomers 2a,b in nearly a 1:1 ratio and the signals of free diamine. The absence
of stereoselectivity in their complexation seems to be a result of the low efficiency of steric interactions between the
benzylaminate palladacycle and the primary amino groups of the diamine (cf. findings of Leung et al.6); it is likely that the
disruption of the agostic interaction iso-Pr. . .Pd in a polar medium may decrease the conformational stability and ability
to chiral recognition of palladacycle as well.
6. Chooi, S. Y. M., Tan, M. K., Leung, P.-H., Mok, K. F., Inorg. Chem., 1994, 33, 3096.
20
7. For (SCRN,SS)-2a·0.3(Stien): m.p. (dec) 204–206°C, [α]D −50.0 (c 1.2, MeOH). Anal. calcd: C, 60.46; H, 6.39; N, 8.69
1
3
for C29.2H36.8ClN3.6Pd. Found: C, 60.57; H, 6.37; N, 8.79. H NMR (DMSO-d6, 40°C; δ, ppm; J, Hz): 1.247 (d, JHH
6.4, 3H, CHMe2), 1.254 (d, 3JHH 6.4, 3H, CHMe2), 1.693 (d, 3JHH 6.6, 3H, α-Me), 3.058 (m, 3JHH 6.4, JCH–NH 4.4, 1H,
3
CHMe2), 3.934 (br.t, JNH–NH 12.1, JNH–CH 9.0, 1H, N2Hax), 4.119 (q, JHH 6.7, 1H, α-CH of palladacycle), 4.222 (m,
2
3
3
1H, α-CH, Stien), 5.147 (br.t, 2JNH–NH 9.0, 3JNH–CH 12.0, 1H, N3Hax), 5.225 (br.d, 2JNH–NH 12.1, 1H, N2Heq), 5.524 (br.d,
2JNH–NH 9.0, 1H, N3Heq), 6.051 (d, 1H, JNH–CH 4.4, N1H of palladacycle), 7.15–7.40 (m, 13H, Ph, η2- and free Stien);
3
aromatic protons of palladacycle: 6.774 (dt, JHH 7.4, 4JHH 1.4, 1H, C5H), 6.911 (dt, 3JHH 7.2, 4JHH 0.8, 1H, C4H), 6.938
3
(dd, 3JHH 7.6, 4JHH 1.6, 1H, C3H), 7.040 (d, 3JHH 7.2, 1H, C6H); free Stien: 3.870 (br.s., 0.6H, α-CH).
8. Kuz’mina, L. G., Burtseva, O. Yu., Porai-Koshits, M. A., Dunina, V. V., Zalevskaya, O. A., Potapov, V. M., Zh. Obshch.
Khim. (Russ.), 1989, 59, 2525–2534 [J. Gen. Chem. USSR, 1989, 59 (Engl. Transl.)].
9. The same (SS)-configuration of both the η2- and µ-bonded Stien ligand was confirmed by 1H NMR: the addition of racemic
diamine to the solution of solvated complex 3a results in the appearance of the signals of the diastereomer (SCRN,RR)-2b.
10. Lifschitz, I., Bos, J. G., Rec. Trav. Chim. Pays-Bas, 1940, 59, 173; Saigo, K., Kubota, N., Takebayashi, Sh., Hasegawa, M.,
Bull. Chem. Soc. Jpn, 1986, 59, 931; Corey, E. J., Lee, D.-H., Sarshar, S., Tetrahedron: Asymmetry, 1995, 6, 3.
11. Pini, D., Inliano, A., Rosini, C., Salvadori, P., Synthesis, 1990, 1023; Shono, T., Kise, N., Oike, H., Yoshimoto, M.,
Ohazaki, E., Tetrahedron Lett., 1992, 33, 5559; Shimizu, M., Kamei, M., Fujisawa, T., Tetrahedron Lett., 1995, 36, 8607.
12. Saigo, K., Kubota, N., Takebayashi, Sh., Hasegawa, M., Bull. Chem. Soc. Jpn, 1986, 59, 931.