270ꢀ CHIMIAꢀ2011,ꢀ65,ꢀNo.ꢀ4ꢀ
Laureates: awards and Honors, sCs FaLL Meeting 2010
Schemeꢀ5.ꢀIMDAꢀ
reactionꢀofꢀtriene 2
withꢀRuꢀcatalystꢀ1a.
O
O
H
5 mol % (R,R)-1a, CH2Cl2
2,6-lutidine, rt, 4 d
(R)-8
2
70% yield
> 95% ee
R2
COR
R2
H
R1
Z
Z
Z
4
5 mol % (S,S)-1b
ROC
3a
7a
R1
2,6-lutidine, CH2Cl2, rt
Z
H
3: R = R1 = R2 = Z = H
9: 92% yield, 84% ee, 99:1 of endo:exo
10: 85% yield, 84% ee, 81:19 of endo:exo
11: low yield and selectivity
4: R = R1 = Z = H, R2 = Me
5: R = Me, R1 = R2 = Z = H
6: R = R2 = H, R1 = Me, Z = CO2Me
7: R = R1 = R2 = H, Z = CO2Me
12: quant., 5864%% ee, 99:1 of endo:exo
84%
13: quant., 56% ee, 99:1 of endo:exo
Fig.ꢀ2.ꢀModelledꢀapproachꢀofꢀtrienalꢀ3
coordinatedꢀtoꢀRuꢀinꢀ(S,S)-1b inꢀanꢀanti-s-trans
orientationꢀ(catalystꢀpartꢀtakenꢀfromꢀtheꢀX-rayꢀ
structureꢀofꢀ[Ru(acetone)((S,S)-BIPHOP-F)
(indenyl)][SbF6]ꢀ((S,S)-1b).[2b]ꢀThisꢀmodelꢀ
rationalizesꢀtheꢀproduct’sꢀ(3aR,4R,7aS)-
configuration.
Schemeꢀ6.ꢀAsymmetricꢀIMDAꢀreactionsꢀcatalyzedꢀbyꢀ(S,S)-1bꢀ(catalystꢀ(S,S)-1a wasꢀlessꢀactive,ꢀ
exceptꢀinꢀtheꢀcaseꢀofꢀtriene 4).[7]
Schemeꢀ7.ꢀSynthesisꢀ
ofꢀhydrazonesꢀ14–17.
OMe
N
N
H
OMe
CHO
H
N
R2
R2
R1
R1
(SAMP)
NH2
Z
Z
Z
Z
MgSO4, 0 oC, CH2Cl2, 2 h
H
H
9: R1 = H, R2 = H, Z = H
14, (95%)
15, (96%)
16, (84%)
17, (86%)
10: R1 = H, R2 = Me, Z = H
12: R1 = Me, R2 = H, Z = CO2Me
13: R1 = H, R2 = H, Z = CO2Me
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