Quim. Nova,
Vol. 26, No. 5, 783-784, 2003
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REAÇÕES ALDÓLICAS ASSIMÉTRICAS CATALÍTICAS
Ivan R. Corrêa Jr. e Ronaldo A. Pilli*
Instituto de Química, Universidade Estadual de Campinas, CP 6154, 13083-970 Campinas - SP
MeO
OSiMe
3+
H
R
O
MeO
R
O
OH
R= Ph, Ph(CH2)2, cC6H11,
(E,E)-CH3CH=CHCH=CH,
Me
3SiO
O
rend. 72-98% % ee 94-98
rend. 72-98% % ee 80-92
O
Me Me
N
O Ti O
O O O tBu
Br
tBu tBu
O
O
O
Me Me
R
OH
Et2O, 0oC 2) nBu
4NF, THF
H
R
O
+
1) 2 mol%
N OTi O
O O O tBu
Br
tBu tBu
Et2O, 0oC 2) nBu
4NF, THF
1) 2 mol%
iPr 3SiC C
Esquema 16
Figura 1
N N
Sn H
Me OTf TfO
H
R H
O N
Sn N Me
O
H R
R O MeH
H
OSiMe3
SEt EtS R
O OSiMe3
Me 1-Nf
Face Si
L*Sn
H
(II)
SEt
OSiMe3 Me
H 2 +
2 +
- L*Sn(OTf)2
L*Sn(OTf)2
2 TfO
-2 TfO
-Figura 2
EtS
OSiMe
3+
H
R
O
EtS
R
O
OSiMe
3R= Ph,
(E)-CH3CH=CH,
(E)-PhCH=CH, C2H5
Sn(OTf)2 (nBu)
2Sn(OAc)2 20 mol%
rend. 46-86%
sin:anti 88:12 a 93:7 % ee (sin) 82-94
OTBS
CH2Cl2, -78oCOTBS
N Pr
N
EtS
OSiMe
3+
H
R
O
EtS
R
O
OSiMe
3rend. 72-88%
sin:anti 91:9 a 99:1 % ee (sin) 95-98
OBn
OBn
Seletividade Sin
Seletividade Anti
Sn(OTf)2 (nBu)
2Sn(OAc)2 20 mol%
CH2Cl2, -78oC
N Pr
N
Esquema 4
784
Corrêa Jr. e Pilli
Quim. Nova
Esquema 21
5 mol%
N P N O
N Me
Me Ph
Ph
1)
2) NaHCO3 aq
R
1OSiCl
3+
H
R
2O
R
1R
2O
OH
R= Ph, tBu, 1-Nf,
(E)-PhCH=CH,
(E)-PhCH=CCH3
rend. 60-98% % ee 52-92 R= Ph, Me, iPr,
nBu, iBu, tBu
CH2Cl2, -78oC
10 mol% N
P N O
N Me
Me Ph
Ph
CH2Cl2, -78oC 1)
2) NaHCO3 aq
OSiCl
3+
H
R
O
R= Ph, 1-Nf,
(E)-PhCH=CH,
(E)-PhCH=CCH3
rend. 90-98%
anti:sin 85:15-99:1 % ee (anti) 82-97
Ph
OSiCl
3+
H
R
O
Ph
R
O
OH
rend. 89-97%
sin:anti 75:25-95:5 % ee (sin) 84-96 10 mol%
N P N O
N Me
Me Ph
Ph
CH2Cl2, -78oC 1)
2) NaHCO3 aq
O
R
OH
Esquema 22
O O H
Cl Si O
-
P(NR2)3Cl O=P(NR2)3
R1
O
O Si H R1
P NR2 NR2 NR2
O Cl
Cl
R1 O OSiCl3
R1 O OSiCl3 ET cadeira
hexacoordenado
ET barco pentacoordenado
anti
sin
+ +
Cl
-Cl -(R2N)3P=O
Figura 9
O O
O O
O O
Li Li
Li Ln
R
1O
+
H
R
2O
R
1R
2O
OH
R= tBu, cC 6H11, iPr, Ph(CH
2)2, PhCH2C(CH3)2
(R)-LLB
(20mol%)
rend. 28-90% % ee 44-94 THF, -20oC
72-277 h R= Ph, 1-Nf,
Me, Et
Esquema 23
Figura 11
Ph
OSiMe
3+
H
R
O
Ph
R
O
OH
R= Ph, 4-ClPh,
C5H11, C8H17, iBu, iPr, 2-Tienil
Pb(OTf)2 (20mol%)
rend. 65-99%
sin:anti 82:18 a 94:6 % ee (sin) 62-87 iPrOH-H
2O (4,5/1)
0oC, 24 h
Me
*
*
OO O
O O
O
