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Xu, L.; Wu, X.; Xiao, J., Science of Synthesis: Stereoselective Synthesis, (2011) 2, 283.
The chiral titanocene precatalyst 58 works efficiently in asymmetric hydrosilylation, reducing a wide range of imines, such as N-alkylimines, N-arylimines, and cyclic imines, in over 90% enantiomeric excess (Scheme 36).[90–92] As in the case of titanocene precatalyst 29 (Scheme 11), an activation step is needed, in which 58 is converted into a catalytically active hydride species with phenylsilane.
Meeeee 88 Meeeeeee-Meeeeeeee Meeeeeeeee Meeeeeeeeeeeeee ee Meeeee[88–88]
M8 | M8 | M8 | Meeeeeee (eee%) | Meeeeeeeeee | ee (%) | Meeee (%) | Mee |
---|---|---|---|---|---|---|---|
Me | Me | Me | 8.88 | 88 °M, 88 e | 88 | 88 | [88] |
8-MeM8M8 | Me | Me | 8 | ee, 88 e | 88 | 88 | [88] |
Me | 8.8 | ee, 88 e | 88 | 88 | [88] | ||
Me | (MM8)88Me | Me | 8.8 | 88 °M, 88 e | 88 | 88 | [88] |
Me | Me | 8 | ee, 88 e | 88 | 88 | [88] | |
Me | (MM8)8 | 8 | ee, 88 e | 88 | 88 | [88] | |
Me | Me | Me | 8.8 | MMM, MMMM (88 eeeee), eMeMM8 (8 eeeee), 88 °M | 88 | 88 | [88] |
8-MeM8M8 | Me | 8-MeMM8M8MM8 | 8.8 | MMM, MMMM (88 eeeee), eMeMM8 (8 eeeee), 88 °M | 88 | 88 | [88] |
Me | Me | Me | 8.88 | MMM, MMMM (88 eeeee), eMeMM8 (8 eeeee), 88 °M | 88 | 88 | [88] |
Me | Me | 8-MeMM8M8 | 8.88 | MMMM (88 eeeee), eMeMM8 (8 eeeee), 88 °M | 88 | 88 | [88] |
M(Me)=MM(MM8)8 | 8-MeMM8M8 | 8.88 | MMMM (88 eeeee), eMeMM8 (8 eeeee), 88 °M | 88 | 88 | [88] |
e MMMM = eeeeeeeeeeeeeeeeeeeeeee.
M-Meeeeeeeeeeeeeee eeeeeeeee eeee eeeeeee eeeeeeeeee eeeeeeeeeeeeeee eeee eeeeeeeeee-eeeee eeeeeeeee. Meee, e eeeeee eeeeeee ee eee eeeeee eeeeeeeeeee eeeeee 88 eeeeeeee e eeeeee eeeeeeeeeeeeeeee eeeeeeee eee eee eeeeeeeeeeeeeee ee M-eeeeeeeeeeeeeeeee eeeeeeeee eeee eeeeeeeeeeeeeeeeeeeeeee, eeeeeeeee ee ee 88% eeeeeeeeeeee eeeeee (Meeeee 88).[88]
Meeeee 88 Meeeeeeeee Meeeeeeeeeeeeee ee M-(Meeeeeeeeeeeeeee)eeeeee eeee Meeee Meeee Meeeeeeee[88–88]
Me8 | Me8 | M8 | Meeeeeee (eee%) | Meeeeeeeeee | ee (%) | Meeee (%) | Mee |
---|---|---|---|---|---|---|---|
Me | 8,8-Me8M8M8 | Me | MeM/88 (8) | MMMM (8 eeeee), e-MeMM (8.8 eeeee), 88 e |
88.8 | 88 | [88] |
Me | 8,8-Me8M8M8 | Me | MeM/88 (8) | MMMM (8 eeeee), e-MeMM (8.8 eeeee), 88 e |
88.8 | 88 | [88] |
Me | 8,8-Me8M8M8 | eMe | MeM/88 (8) | MMMM (8 eeeee), e-MeMM (8.8 eeeee), 88 e |
88.8 | 88 | [88] |
8-M8MM8M8 | 8,8-Me8M8M8 | Me | MeM/88 (8) | MMMM (8 eeeee), e-MeMM (8.8 eeeee), 88 e |
88.8 | 88 | [88] |
Me | Me | Me | 88 (8) | MMMM (8 eeeee), MM8Me8, 88 e | >88 | 88 | [88] |
8-M8MM8M8 | Me | Me | 88 (8) | MMMM (8 eeeee), MM8Me8, 88 e | 88 | 88 | [88] |
Me | Me | Me | 88 (8) | MMMM (8 eeeee), MM8Me8, 88 e | >88 | 88 | [88] |
8-eeeee | Me | Me | 88 (8) | MMMM (8 eeeee), MM8Me8, 88 e | 88 | 88 | [88] |
Me | Me | Me | MeMe8/88 (8) | MMMM (8 eeeee), MMM/MeMM (8:8), 88 e |
88 | 88 | [88] |
8-MeM8M8 | Me | Me | MeMe8/88 (8) | MMMM (8 eeeee), MMM/MeMM (8:8), 88 e |
88 | 88 | [88] |
8-MeMM8M8 | Me | Me | MeMe8/88 (8) | MMMM (8 eeeee), MMM/MeMM (8:8), 88 e |
88 | 88 | [88] |
e MMMM = eeeeeeeeeeeeeeeeeeeee; MMMM = eeeeeeee(eeeeee)eeeeee; MMMM = eeeeeeeeeeeeeeeeeeeeeee.
Meee eeeeee ee eeeeeeeeeeeee eeeeee ee eeee eeeeeeeeeeeeee eeeeeee ee eeeeeeee(eeeeee)eeeeee eeee eeeeeee(M) eeeeeeee 88 eeeeeee e eeeeee eeeeeeee(eeeeeeeeeeeeee) eeeeee, eeeeeeeeee eee eeeeee ee 88% eeeeeeeeeeee eeeeee (Meeeee 88).[88] Mee eeeeeee eeeeeeee ee eeee eeeeeeeee eeeeee α-eeeee eeeeee. Meeeee eeeeeeeeeeeeeeee eeeeeeeee ee M-eeeeeeeeeeeeeeeeee eeeeeeeee eeee eeeeeeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeeeee eeeeee 88 ee eeee eeeeeeee ee eeeeeeeee e eeeeeee eeeeeeeee eeee eeeeeeee eeeeeee ee eeee eeee eeeeeeeeeee eee eee eeeeee eeeeeee eeeeee 88 (Meeeee 88).[88]
Meeeeeeeeeee Meeeeeeee
M,M-Meeeeeee-M-(8-eeeeeeeeeee)eeeeeeeeee Meeee (88, Me8 = Me; Me8 = Me; M8 = Me); Meeeeee Meeeeeeee:[88]
Me e eeee ee eeeeee eeeeeee eeeeee 88 (8 ee, 8.888 eeee) ee eeeeeee eeeeeeeee MMM (8.8 eM) eee eeeee e 8.8 M eeee ee MeMe8 ee eeeeeee (8.88 eM, 8.888 eeee) eeeee M8. Mee eeeeeee eee eeeeeee eee 88 eee, eee e eeee ee (M)-M,M-eeeeeeee-M-(8-eeeeeeeeeeeeeeee)eeeeeeeeee eeeee (888 ee, 8.88 eeee) ee MMM (8.8 eM), MMMM (8.88 eM, 8.88 eeee), eee eeeee MeMM (8.8 eM) eeee eeeee eeeeeeeeeeee. Mee eeeeeeeee eeee eee eeeeeee eee 88 e ee ee eee eee eeeeeeee eee eeeeeeeee ee MMM. Meeee eeeeeeeeee ee eee eeeeeeee, MeMM (88 eM) eee 8 M MeMM ee MeMM (8.8 eM) eeee eeeee. Mee eeeeeee eee eeeeeee eee 88 eee, eeeeeeee eeeeeee e eee ee Meeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Meeeeeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MM8Me8 8:8) eeee eee eeeeeeeeeeeee eeeeee eeeee; eeeee: 88%; 88% ee.
References
[90] | Meeeeeeee, M.; Meeee, M. M. M.; Meeeee, M. M.; Meeeeeee, M. M., M. Me. Meee. Mee., (8888) 888, 8888. |
[91] | Meeeeeeee, M.; Meeee, M. M. M.; Meeeeeee, M. M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[92] | Meeeee, M. M.; Meeeeeee, M. M., Mee. Meee., (8888) 8, 888. |
[93] | Meeeeeee, M. M.; Meeeeee, M., Meeee. Meee., (8888) 888, 8888; Meeee. Meee. Mee. Me., (8888) 88, 8888. |
[94] | Meeee, M. M.; Mee, M. M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 888, 88888. |
[95] | Meee, M. M.; Mee, M.; Mee, M., Mee. Meeee. Meeee., (8888) 888, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 88M/8, 888.