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Yliniemelä-Sipari, S. M.; Pihko, P. M., Science of Synthesis: Stereoselective Synthesis, (2011) 2, 662.
Shibasakiʼs first-generation catalyst (S)-22 [(S)-LLB] was the first catalyst within the category of bifunctional multimetallic asymmetric catalysis that was shown to promote nitroaldol reactions of unmodified nitroalkanes with a variety of aldehydes with good yields and enantioselectivities (Scheme 44).[178] Preparation of the catalyst 22 can be performed by treatment of lanthanum(III) isopropoxide with the lithium salt of 1,1′-binaphthalene-2,2′-diol (BINOL) in the presence of a small amount of water, although equally active catalyst can be prepared by several alternative procedures.[179,180] The complex maintains its activity for several months if stored under argon at ambient temperature, and special precautions for its handling are not necessary. The nitroaldol reaction using the first-generation catalyst (R)-22 [(R)-LLB] has been successfully used as key step in the synthesis of β-blockers[179,181,182] and allo-phenylnorstatine.[183]
Meeeee 88 Meeeeeeeee Meeeeeeeee Meeeeeeee Meeeeeeee ee e Meeeeeeee Meeeeee[888]
M8 | ee (%) | Meeee (%) | Mee |
---|---|---|---|
eMe | 88 | 88 | [888] |
Me | 88 | 88 | [888] |
(MM8)8Me | 88 | 88 | [888] |
Meeeeee eeeeeeeeee eeeeeeeeeeeee ee eee eeeeeeee eeee eeee eeeeeeee eeeeeee eeeeeeeeeeee ee eee 8,8′-eeeeeeeee ee eee (M)-8,8′-eeeeeeeeeeeee-8,8′-eeee eeeeeeee, eeeee eeeeee ee eeeeeeee eeeeeee- eee eee/eeee-eeeeeeeeeeeee (Meeeee 88). Meeeeeee 888 (M = M≡MMMM) eeeeeeee eee eeee eeeeeee (eee/eeee eeeeee ee eeee ee 88:8, ee ee 88% ee, eee eeeeee eeeeeeeee).[888] Meee eeeeeeee eeeeeeee eee eeee eeeeeee ee eee eeeeeeeee eeeeeeeee ee eeeee-eeeeeeeeeeeeeeeeee.[888]
Meeeee 88 Meeeeeeee- eee Meeeeeeeeeeeeeee Meeeeeeeee Meeeeeeee Meeeeeeee ee Meeeeee Meeeeeeee Meeeeeeee[888]
M8 | M8 | M | ee (eee/eeee) | ee (%) (eee) | Meeee (%) | Mee |
---|---|---|---|---|---|---|
(MM8)8Me | Me | M | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | Me | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | M≡MM | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | M≡MMMM | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | M≡MMMM | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | M≡MMMM | 88:8 | 88 | 88 | [888] |
(MM8)8Me | Me | M | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | M≡MMMM | 88:8 | 88 | 88 | [888] |
(MM8)8Me | MM8MM | M | 88:88 | 88 | 88 | [888] |
(MM8)8Me | MM8MM | M≡MMMM | 88:8 | 88 | 88 | [888] |
(MM8)8Me | MM8MM | M | 88:88 | 88 | 88 | [888] |
(MM8)8Me | MM8MM | M≡MMMM | 88:8 | 88 | 88 | [888] |
Me eeeeeee eeeeeee eeeeeeee eeeee eee eeeee eeeeeeee eeeeeeee, e eeee eeeee eeeeee-eeeeeeeeee eeeeeeeee eeeeeeee eeeeee eee eeee eeeeeeeee, eeeeeeee eeee 88 ee 888 (M = M≡MMMM), eeeee (8 eeeee eeeeeeee ee Me), eee eeeeeeeeeeee (8.8 eeeee eeeeeeee ee Me). Meee eeeeeeee eeeeee eeeeeeeeeee eeeeeeee eeeeeeeee eeeeeeeeee eeeeeeeeee eeeeeeeee eeeeeee eeeeeeeee 888 eee eeeeeeeeeeee 888 ee eeee eeeeeeee 888, eeee eeee e eeeeeee eeeeeeee eeeeeee (8 eee%) (Meeeee 88).[888] Mee eeee eeeeeeeeeee ee eeeeeeeeee eeeeeeeee ee eeeeeeeeee ee eeeeee eeeeeeeee ee eeeeeeeee 888 eeeeeee eeeeee eeeeeeee, eeeee ee eeeeeeee ee ee eee eeee-eeeeeeee eeee ee eee eeeeeeeee eeeee (Meeeee 88).
Meeeee 88 Meeeeeeeee ee eee Meeeeeeee Meeeeeeee Meeeeeee/Meeeeeeeeee ee Meeee- eee Meeeee-Meeeeeeeee Meeeeeeee Meeeeeeee[888]
M8 | M8 | Meeeeeee | Meee (e) | Meee (°M) | ee (eee/eeee) | ee (%) ee eee | Meeee (%) | Mee |
---|---|---|---|---|---|---|---|---|
Me | M | 88 | 88 | −88 | – | 88 | 8.8 | [888] |
Me | M | 88/MeMe/M8M | 88 | −88 | – | 88 | 88 | [888] |
(MM8)8Me | Me | 888 (M = M≡MMMM) | 888 | −88 | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | 888 (M = M≡MMMM)/MeMe/M8M | 888 | −88 | 88:88 | 88 | 88 | [888] |
(MM8)8Me | Me | 888 (M = M≡MMMM) | 888 | −88 | – | – | eeeee | [888] |
(MM8)8Me | Me | 888 (M = M≡MMMM)/MeMe/M8M | 888 | −88 | 88:8 | 88 | 88 | [888] |
(MM8)8Me | MM8MM | 888 (M = M≡MMMM) | 888 | −88 | – | – | eeeee | [888] |
(MM8)8Me | MM8MM | 888 (M = M≡MMMM)/MeMe/M8M | 888 | −88 | 88:8 | 88 | 88 | [888] |
Meeeee 88 Meeeeeee Meeeeeeee eee Meeeeeeeee Meeeeeeeee Meeeeeeee Meeeeeeee ee Meeee- eee Meeeee-Meeeeeeeee Meeeeeeee Meeeeeeee[888]
Me eeee-eeeeeeeee eeeeeeeee eeeeeeeeee eeeeeeeeee eeeeeeee eeeeeeee ee e eeeeeeeeeeeeeeee eeeeeeeee/eeeeee eeeeeee eeee ee eeeee-eeeee eeeeee eee eeee eeeeeeee.[888] Meeeeeee eeeeeeeeee eeeeeeee eee eeeeeeee ee e eeeeee eeee-eeeeeeeee (ee ee >88:8) eee eeeeeeeeeeeeeeee eeeeee (ee ee 88%), eee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeee/eeeeee eeeeeee eeeeeeee e eeeeeeeee eeeeeeeee.
Meeeeeeeeeee Meeeeeeee
(8M,8M)-8-Meeee-8-eeeeeeeeeee-8-ee [888, M8 = (MM8)8Me; M8 = Me]; Meeeeee Meeeeeeee Meeee eee Meeeee-Meeeeeeeee Meeeeeee 888 (M = M≡MMMM):[888]
MMMMMMM: Meeeeeeeeeee eeeeee eeeeeeeee eeee eeeee, eeeeeeeeee eeeeeeeee eeeeeeeee eeeee eee eeeeeee eeee eeeeeeeeeeeee ee eeeeeee ee eee. Me eeeeee eeeeee eeee eeeee ee eee eeeeee. Meeeeeee ee eeeee eeeee ee eeee eee ee eeeeee.
Meeeeeeeeee ee eee eeeeee-eeeeeeeeee eeeeeeee: Me e eeee ee (M)-8,8′-eee[(eeeeeeeeeeeee)eeeeeee]-8,8′-eeeeeeeeeeeee-8,8′-eeee (8.88 e, 8.8 eeee) eee MMM (88 eM) eee eeeee e eeee ee Me(MeMe)8 (8.8 eeee) ee MMM (8 eM) eeee eeeeeeee ee 8 °M eeeee ee eeeee eeeeeeeeee. Me eee eeeeeeeee eeeeeee eee eeeee e eeee ee MeMe ee eeeeee (8.88 eM, 8.8 eeee) ee 8 °M. Meeee 88 e ee eeeeeeee ee ee, M8M (8.8 eeee) ee MMM (8 eM) eee MeMe (8.8 eeee) ee eeeeee (8.88 eM) eeee eeeee ee eeeeee e eeeee eeeeee eeee ee eee eeeeeeee
Meeeeeeeee eeeeeeeeee eeeeeeeee: Me e eeee ee eee eeeeeeee eeeeeeee ee eeeee (8.88 eM, 8.8 eeee) eee MMM (8.88 eM) eee eeeee eeeeeeeeeeee (888, M8 = Me; 8.88 eM, 8.8 eeee) ee −88 °M eeeee ee eeeee eeeeeeeeee, eee eee eeeeeeeee eeeeeee eee eeeeeee eee 8.8 e ee eee eeee eeeeeeeeeee. Meeeeeee 888 [M8 = (MM8)8Me; 8.88 eM, 8.88 eeee] eee eeeee, eee eeeeeeee eee eeeeeeeee eee 888 e ee −88 °M. Mee eeeeeee eee eeeeeee eeee 8 M MMe (8 eM) eee eeee eeeeeeeee eeee Me8M (8 × 88 eM), eee eee eeeeeeee eeee eeeeee eeee eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeee 8:88) ee eeeeee eee eeeeeeeeee eeeeee 888 [M8 = (MM8)8Me; M8 = Me]; eeeee: 88 ee (88%); 88% ee; ee (eee/eeee) 88:8.
References
[178] | Meeee, M.; Meeeee, M.; Meee, M.; Meee, M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
[179] | Meeee, M.; Meeeee, M.; Meee, M.; Meeeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 888. |
[180] | Meeee, M.; Meeeeeee, M.; Meeeeeeee, M., Meeeeeeeee, (8888) 8, 888. |
[181] | Meeee, M.; Meeeee, M. M. M.; Meeeee, M.; Meeeeeeee, M., Meeeeeeeeee, (8888) 88, 88888. |
[182] | Meeee, M.; Meeeee, M.; Meee, M.; Meeeeeeee, M., Meee. Meeeeeeee. Meee., (8888) 8, 888. |
[183] | Meeee, M.; Mee, M.-M.; Meeeee, M.; Meeeeeeee, M.; Meeeeee, M.; Meeeeeee, M.; Meeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[184] | Meeee, M.; Meeeeeee, M.; Meeeeeee, M.; Meeeee, M.; Meee, M.; Meeeeeeee, M., M. Mee. Meee., (8888), 88 8888. |
[185] | Meee, M.; Meeeee, M. M. M.; Meeeeeee, M.; Meeee, M.; Meeeeeeee, M., Meee.–Mee. M., (8888) 8, 8888. |
[186] | Meeeeeee, M.; Meeeee, M.; Meeeeeeee, M.; Meeeeee, M.; Meeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 88888. |