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Han, J. W.; Hayashi, T., Science of Synthesis: Stereoselective Synthesis, (2011) 1, 923.
General Introduction
Palladium-catalyzed asymmetric hydrosilylation of C=C bonds is one of the most efficient methodologies to give enantiomerically enriched organosilicon compounds, which are useful intermediates in stereoselective organic synthesis.[1–6] The hydrosilylation of simple alkenes, such as styrene and oct-1-ene with trichlorosilane, provides chiral alkylsilanes 1, which are transformed into chiral alcohols 2 by way of oxidative cleavage with retention of configuration, and that of conjugated 1,3-dienes provides chiral allylsilanes 3, which are transformed into chiral homoallylic alcohols 4 by way of the diastereoselective reaction with carbonyl compounds (Scheme 1).[7–10] In addition, double hydrosilylation of norbornadiene followed by oxidation provides enantiomerically enriched diol 5, which is a versatile intermediate for asymmetric synthesis of useful chiral molecules, such as (+)-sparteine (6) and chiral norbornadiene ligand 7 (Scheme 1).[11–13]
Meeeee 8 Meeeee Meeeeee ee Meeeeeeeee Meeeeeeeeeeeeee[8–88]
Mee eeeeeeeee-eeeeeeeee eeeeeeeeee eeeeeeeeeeeeeee ee M=M eeeee eee eeee eeeeeeee eeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeeeee eeeeeeeee, eee ee eeee e eeee eeee-eeeeeeeee eeeeeeee, eeeee ee ee ee eeeeeeee eeeeeee eee eeeeeee eeeeeeee eeee e eee eeeeeeee eeeeeee eee eeeeeee eee eeeeeee. Meeeeee, eeee eeeeee ee eeeee ee e eeeee-eeeee eeeeeeeeeee ee eeeeee eeeeeeeeeeeee eee ee eee eeeeeeeeee eeeeee ee eee eeeeeeee eee eee eee ee eeeeeeee eeeeeeeeeeeeeee (ee 88 °M).[88]
Me eee eeeeee ee e eeeee ee eeeeeeeee-eeeeeeeee eeeeeeeeee eeeeeeeeeeeeeee ee eeeeeee, eeeeeee eeeeee eeeeeeeeeee eeeeeeeee eeeeeee eeee eeee eeeeeeeee eee eeeeeeeee eeee eeeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeeeeeee. Meeeeee, eee ee e eeeeeeeee eeeeeeeeeeee eeeeee, eeee ee 8,8′-eee(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee (8), eeeee ee eeeee eeeeeeeee eeeeeeee eeee eee ee eeeeeeeeeee eeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeee.[88] Mee MMM eeeeeee 8–88, eeeeee eeeeeeeeee eeeee eeeeeeeee,[88,88] eeeeeeeeee eeeeeee 88–88, eeeeee eeeeee eeeeeeeee,[88–88] eee eeeeeeeeeeeeeee eeeeee 88, eeeeee e eeeeeeeeee eeeeee,[88] eeeeee eeee eeeeeeeee eeeeeeeeee eee eeeeeeeeeeeeeeeeeeee ee eee eeeeeeee (Meeeee 8).
Meeeee 8 8,8′-Mee(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee eee Meeeee Meeeeeeeeee Meeeeeeee eee Meeeeeeeeeeeeee Meeeeee eee Meeeeeeeeeeeeee[88–88]
Meeee eeeee eeeeee eeeeeeeeeee eeeeeeeee eeeeeee, MMM eeeeeee 8–88 eeeee eee, eeeee eeee eee eeeeeee eeeeeee ee eeeeeeeeeee ee eeeeeeeeeee eeeee ee eee 8′-eeeeeeee ee eee eeeeeeeeee eeeeeeee; ee eeeeeeee, eeeee eee eee eeeeeeee eee eeeeeeeee eeeee. Mee eeeeeeeeeee eeeeeee ee eee eeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeee/MMM eeeeeeeee ee eeee eee eeeeeeeeeeeeeeeeeeee eeee eeeeeeeeeeee eeeeeeeee ee eee eeeeeeeee eeee, eeeeeeee eee eeeeeeeee eeeeeeee eeee eee eeeeee eeee eeee (Meeee 8). Mee eeeeeee, 8-(eeeeeeeeeeeeeeeee)-8′-eeeeeee-8,8′-eeeeeeeeee (8, MeM-MMM), eeeee ee eee eeee eeeeee eee eeeee-eeeeeeeeeee eeeeeee, eeeeeee eeee eeeee eeeeeeeeeeeeeeeeee eeee 8-(eeeeeeeeeeeeeeeee)-8,8′-eeeeeeeeee (88, M-MMM) ee eee eeeeeeeeeeeeeee ee eeeeeee (Meeee 8, eeeeeee 8 eee 8).[88,88,88] Me eee eeee ee eee eeeeeeeeeeeeeee ee eeeeeeeeeeeeeee, 8-(eeeeeeeeeeeeeeeee)-8′-(8,8-eeeeeeee-8-eeeeeeeeeeeee)-8,8′-eeeeeeeeee (88, Me-MMM) eeeee eeee eeeeee eeeeeeeeeeeeeeeeee eeee MeM-MMM (8) eee M-MMM (88) (eeeeeee 8–8).[88,88]
Meeee 8 Meeeeeeee-Meeeeeeee Meeeeeeeee Meeeeeeeeeeeeee ee M=M Meeee eeee Meeeeeeeeeeeeee Meeee MMM Meeeeee[88,88–88]
Meeee | M8 | M8 | MMM Meeeee | Meee (°M) | Meee (e) | ee (%) | Meeee (%) | Mee |
---|---|---|---|---|---|---|---|---|
8 | Me | M | 8 | 8 | 88 | 88 | 888 | [88] |
8 | Me | M | 88 | −88 | 88 | 88 | 88 | [88] |
8 | (MM8)8Me | M | 8 | 88 | 88 | 88 | 88 | [88] |
8 | 8 | 88 | 88 | 88 | 888 | [88] | ||
8 | 88 | 88 | 8 | 88 | 88 | [88] | ||
8 | 88 | 8 | 88 | 88 | 88 | [88] |
References
[1] | Meeeeee, M.; Meeeeeee, M., Me Meeeeeeeeeeee Meeeeeeeeeeeee Meeeeeeee MMM, Meeeeeee, M. M.; Meeeee, M. M. M., Mee.; Meeeeeee: Meeeee, (8888); Mee. 88, e 888. |
[2] | Meeeee, M. M.; Mee, M.; Meee, M. M., Meee. Mee., (8888) 888, 8888. |
[3] | Meeeeeee, M.; Meeeeee, M., Me Meeeeeeeee Meeeee eee Meeeeee Meeeeeeee, 8ee ee., Meeeee, M.; Meee, M., Mee.; Meeee-MMM: Meeeeeee, Meeeeee, (8888); Mee. 8, e 888. |
[4] | Meeeeee, M., Me Meeeeeeeeeeee Meeeeeeeee Meeeeeeee, Meeeeeee, M. M.; Meeeee, M.; Meeeeeee, M., Mee.; Meeeeeee: Meeeee, (8888); Mee. 8, e 888. |
[5] | Mee, M. M.; Meeeeee, M., Me Meeeeeeee Meeeeeeeee Meeeeeeee, 8ee ee., Meeee, M., Me.; Meeee-MMM: Mee Meee, (8888); e 888. |
[6] | Meeee, M., Me Mee Meeeeeeee ee Meeeeee Meeeeee Meeeeeeee, Meeee, M.; Meeeeeeee, M., Mee.; Meeee: Meeeeeeeee, MM, (8888); e 8888. |
[7] | Meeee, M., Mee. Meeeeee Meee., (8888) 8, 8. |
[8] | Meeeeeeee, M.; Meeeeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[9] | Meeee, M. M.; Meeee, M. M., Meee. Mee., (8888) 88, 8888. |
[10] | Meeeeeeee, M.; Meeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[11] | Meeeeeeee, M.; Meeeöeee, M.; Meeeee, M. M.; Meeeeeeee, M.; Meee, M.; Mee, M.; Meeeöeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[12] | Meeee, M. M.; Meeee, M. M.; Meeé, M., Mee. Meee., (8888) 8, 8888. |
[13] | Meeeeee, M.; Meeeee, M.; Meeeeeee, M.; Meeeeee, M., M. Me. Meee. Mee., (8888) 888, 88888. |
[14] | Meeeee, M.; Meeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[15] | Meeeeee, M., Mee. Meee. Mee., (8888) 88, 888. |
[16] | Meeeee, M.; Meeeeeeee, M.; Meeeeee, M., Mee. Meeee., Meee. Mee. M, (8888), 888. |
[17] | Meeee, M.; Meeee, M., Meeeeeeeeee: Meeeeeeee, (8888) 8, 8888. |
[18] | Meeeeeee, M. M.; Meeeeeeee, M., M. Mee. Meee., (8888) 88, 8888. |
[19] | Mee, M. M.; Meeeeeee, M.; Meeeeee, M., Meee. Meee. Meee, (8888) 88, 8888. |
[20] | Meeeee, M. M.; Meeeeeee, M. M.; ee Meee, M. M.; Meeeeeee, M. M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[21] | Meeeee, M.; Meeeeeee, M.; Meeeeee, M., Meeeeeeeeee: Meeeeeeee, (8888) 8, 8888. |
[22] | Meeeeeee, M.; Meeeee, M.; Meeeeee, M., M. Meee. Mee., Meee. Meeeee., (8888), 8888. |
[23] | Meeeeeee, M.; Meeee, M.; Meeeee, M.; Meeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[24] | Meeeeee, M.; Mee, M. M.; Meeeee, M.; Meee, M.; Meeee, M.; Meeeeee, M.; Meeee, M.; Meeeee, M., Mee. Meeee. Meeee., (8888) 888, 888. |