ON
1) 2SmI2 ,THF 2) H O+
3
O NH2
Possible Mechanism:
+ 2+
RX
Sm
RX-.
+ 2+
R
Sm
R + SH
(Solvent)
R + SH
. + RX-
3+
Sm
R +X
+ R
3+
Sm
. RH + S
RH + S
R
+ 2+
O
Sm
R
R. CO R
+
+
H
(or SH)
+ 1
RN3
2
RCN
1 . 2 SmI2/ THF 2. 10% K2CO3
H 1N
R2
R
NH
1
RN3
SmI2
.1
RN SmI2
2
RCN
SmI2
1
RN
R2
N2
N.
SmI2
SmI2
1
RN
R2
H2 O
1
HRN
R2
NSmI2
NH
Yield: 60-72%
J. Chem. Res.(s), 2001, 32
_
SmI2
ArX + PhZ THF-DMF
ArZPh + X
ArX=PhI, 1-BrPh, 1-BrAdm, 2-ClQuin
_
_
_
_
_
PhZ =PhSe , PhCH2Se , PhTe , PhS
Heteroatom Chem. 2001, 12, 539
O ArC Cl
1
SmI2
ArCO2
OSmI2
+
H
R
OH R
SmI2、SmI3促进的有机反应
SmI2 PhCOCH2Br THF
1. RCHO 2. H2O
O Ph
H
H R
SmI2 PhCOCH2Br -SmI2Br
_ Sm(III)/I PhCOCH2Br
O
.
Ph CH2
Sm(III) _
O
I
Br Ph
SmI2 -IBr
OSm(III) Ph
+ O
Ph
R1
2.2SmI2 Ph RCN THF, reflux R1
O
OH OH
R + Ph
Ph
OH
R1 R 1
O
Ph
R1
. SmI2
OSm2 R2CN
Ph R SmI2
Ph
OSmI2 R2
R1 NSmI2
H2O, HCl
Ph R1
H2O, HCl
O
R2 OH
I2SmO OSmI1
Ph
Ph
R1 R 1
R. + 2+ C OH Sm
R
R
C
OH
+
+
H
R
(or SH)
R. CO R
+ 3+
Sm
R. C OH R
R
+ C OH
3+
Sm
R
RH C
R OH
RX +
SmI2
R+
O
SmI2
SmI2
OSmI2
.
+
H
OH
R
OSmI2 R
RX + SmI2
R + SmI2
O
RSmI2 +
R + SmI2X
RSmI2
n-C12H25I n-C12H25OTs
2SmI2 2SmI2
+ n-C4H9I
n-C6H13COCH3
n-C12H26
n-C12H26
2SmI2
CH3 n-C6H13C n-C4H9
OH
PhCH2Br 2SmI2 PhCH2CH2Ph
PhCH2CH CH2 O
2SmI2 PhCH2CH CH2
CH3CN Ar
2
O2CAr Ar
Yield: 70-85% cis:/trans 90/10-95/5
O
SmI2
Ar C Cl
O
Ar C .
O
OO Ar C C Ar SmI2
2 SmI2 Ar C-
O
Ar CC........O_...
Ar
O
Ar
O
Sm I SmI2
C
2-
C
Ar
O
A
B
Ar O C Ar Sm I 2ArCOCl C
活泼金属参与的有机合成反应
Mediate Promote Catalyst
活泼金属参与的有机反应
1、还原反应
Metal
NO2
NH2
R
H+
R
M = Zn Fe Sn
R
Na
R
R
NH3(l)
R
Claimenson Reduction
O
R
R'
Zn-Hg H+
O
R
R'
R
R'
Zn
RBr
mechanism
ArNO2 2 SmI2
. . ArNO
SmI2
RCN ArN OSmI2
Ar
OSmI2
N
N
SmI2
I2SmOSmI2
R
Ar
OSmI2
N
N
SmI2 2 SmI2
Ar
SmI2 N
N SmI2 OH2
R
R
I2SmOSmI2
ArNH R NH
J. Chem. Soc. Perkin Trans. 1, 1998, 2899
H2O, HCl C
OH OH
Ph
Ph
R1 R 1
Tetrahedron Lett. 1998, 39, 8491
SRN1 Reaction of Haloarenes with Benzenethiolate, Benzeneselenolate, and
Benzenetellurolate ions Promoted by SmI2
-I2
_ I PhCOCH2Br
O Ph
_ Sm(III)/I
O
Sm(III)
_ I
I
I
Ph
Synth. Commun. 1988, 18, 2003
O
1
R
X + R3CHO SmI3
THF
R2
X=Br, COCH3, COOCH3
OH
1
R
R3
R2
Tetrahedron Lett. 1993, 24, 4547
O
+ Br
R
R'
Metal H2O
OH R'
R
M = Bi Al In Sm Sn
金属钐参与的有机反应
E0 aq Sm3+/Sm2+ = -1.55V
Kagan:
+ Ln ICH2CH2I THF
+ LnI2 H2C CH2
Ln=Sm, Yb
n-C7H15CHO
2SmI2
n-C7H15CH2OH
R'
R'
2、还原偶联反应
Mg or Sm
O
toluene
HO OH
3、Grinard 反应
Mg
RX
ether
R Mg X
O
R Mg X +
R''
R'
OH
R''
R'
R
4、Reformatsky 反应
X
OEt
Zn
R
ether
O
OH
R''
R'
OEt
R
O
ZnX OEt
R
O
O
R'' R'
5、Barbier 反应
C Ar O C Ar
O C
Chin. J. Chem. 2001, 19, 634
金属钐/辅助试剂促进的有机反应
Sm/I2 (cat)体系
RSSO3Na
Sm/Cat. I2 THF, r.t.
RSSR
Synth. Commun., 1997, 27 ,1043
RN3
Sm/Cat. I2 MeOH, N2, r.t. or reflux
O C6H5CCH2Br SmI2 or SmI3
RCOCl
OOO
OO
C6H5 H H
R OO
C6H5 COOH
Tetrahedron Lett., 1996, 37, 3885
+ R1NO2
R2CN 1.SmI2 (6 eq.), THF, r.t. 2. 10% K2CO3
H R1 N
R2
NH