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I.P. BeletskayaChemistry Department of Moscow State University, Moscow, Russia
Transition metal complexes - the catalysts of organic reactions
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Transition metal catalysis in industry
MeOH + CO MeCO2H
RCH=CH2 + CO H2 RCH2CH2CHO
CH2=CH2 + O2 CH3CHO
CH2=CHCH=CH2 + 2HCN NC(CH2)4CN
RCH=CH2 -[CRH-CH2]-
RCH=CH2 + H2 RCH2CH3
Rh,
Co, Rh
Pd with Cu
Ni
Ti, Zr, V
Rh, Ru
RhCl(PPh3)3, RhCl(CO)(PPh3)2, RhH(CO)(PPh3)2, [RhCl(C2H4)2]2, [RhCl(CO)2]2, PdCl2(MeCN)2,
PdCl2(PPh3)2, Pd(PPh3)4, [Pd(OAc)2]3, Pt(PPh3)4, Pt(PPh3)3, Cp2Co, Co2(CO)8, NiCl2(PPh3)2,
NiCl2dppm,NiCl2dppe, NiCl2dppp, NiCl2dppb, NiCl2diop, Ni(COD)2, IrCl(CO)(PPh3)2, RuCl2(PPh3)3
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Transition metal catalysis in industry
MeOH + CO MeCO2H
RCH=CH2 + CO H2 RCH2CH2CHO
CH2=CH2 + O2 CH3CHO
CH2=CHCH=CH2 + 2HCN NC(CH2)4CN
RCH=CH2 -[CRH-CH2]-
RCH=CH2 + H2 RCH2CH3
Rh,
Co, Rh
Pd with Cu
Ni
Ti, Zr, V
Rh, Ru
RhCl(PPh3)3, RhCl(CO)(PPh3)2, RhH(CO)(PPh3)2, [RhCl(C2H4)2]2, [RhCl(CO)2]2, PdCl2(MeCN)2,
PdCl2(PPh3)2, Pd(PPh3)4, [Pd(OAc)2]3, Pt(PPh3)4, Pt(PPh3)3, Cp2Co, Co2(CO)8, NiCl2(PPh3)2,
NiCl2dppm,NiCl2dppe, NiCl2dppp, NiCl2dppb, NiCl2diop, Ni(COD)2, IrCl(CO)(PPh3)2, RuCl2(PPh3)3
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Discovered : by W.H. Wollaston in 1803
Isolated in London, UK
Origin : The element is named after the
asteriod Pallas, also discovered in 1803.
Pallas was the Greek goddess of
wisdom.
Palladium
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R M R' X+ R R' R' = Alk Wurtz
R M Ar (Het), vinyl, alkynyl R Ar (Het), vinyl, alkynyl
Kumada, Corriu (1972)
+cat
cat = Ni, Pd
aryl aryl (Ar-Ar, Ar-Het, Het-Het)
aryl alkenyl (Ar , Het )
R R
alkenyl alkenyl
aryl alkynyl (Ar R, Het R)
alkenyl alkynyl
aryl alkyl
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Cross-coupling reactions
R Hal(OTf) + R R'
R=Ar, Vinyl; R'=Ar, Vinyl, Alk
R' M[Pd]
M = MgX (Tamao - Kumada)
= SnR3 (Migita - Kosugi - Stille)
= ZnX (Negishi)
= B(OH)2 (Suzuki - Miyaura)
= SiR3 (Hiyama)
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R Hal(OTf) R R'R'[Pd], Cu
+
R=Ar, Vinyl; R'=Ar, Alk
base
Sonogashira - Hagihara
Cross-coupling reactions
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Mizoroki-Heck reaction
RHal(OTf) +Z
[Pd]base
R
Z
R = Ar, vinylZ = Ar, COOH, COOR, CN
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Carbonylation
R Hal +
R=Ar, Vinyl; HNu = H2O, ROH, RNH2, R2NH, RSH
R' M[Pd]
+ COR R'
O
R Hal + HNu[Pd]
+ COR Nu
Obase
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Pd-catalyzed reactions
+ Pd(0)
R
X
Sonogashira
coupling
R'
R
H-E
(H-P,H-S, H-Se)
E
R
Buchwald - Hartwig
amination
HNR2'
R
NR2
(Nu=OH, OR,NR2)R
CONu
CO, Nu
Miyaura-Suzuki
coupling
R
Ar
ArB(OH)2
HC
Y
Z
R
CH
Y Z
Mizoroki-Heck
reaction
R
R'
R' CN
R
CN
R
PdX
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Pd
R'
X
Pd
R'
X
RM
Pd(0) or Pd(II) precatalyst
L
L
L LPd
R'
R
Pd
R'
RL
L
L L
PdL2
R'X
RR'
catalyst pre-activation
oxidativeaddition
reductiveelimination
transmetalation
Pd metal
deactivation
L
Catalytic cycle of Pd-catalyzed reactions
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Reactions in water or aq. solution (ligandless)
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Stille reaction
Z
N2 X
+ Me4SnPd(OAc)2
MeCN:H2O, rt
Z
Z: o-, p-NO2, p-Br,
p-MeO, p-Me
Z
I X
+ RSnMe3
Pd(OAc)2
H2O, 60oC
Z
R
2
R: Me, m-MeC6H4
Z: H, m-NO2
Izv. Akad. Nauk SSSR, Ser. Khim., 1990, 2665; 1992, 2683
Z
X
+ RSnPdCl2 or PdCl2L2
H2O, 100oC
Z
R
X: Br, I
Z: m-CO2H, p-OH, p-Ac,
p-Me, o-NH2, o-OCH2CO2H
R: Me, Ph, etc.
[RSn]: RSnCl3, Kn[RSn(OH)3+n]
L: TPPMS Ph2P
SO3M
Tetrahedron Lett., 1995, 36, 125
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Suzuki-Miyaura reaction
ArB(OH)2 +cat
basesolvent
Ar'(Het)X Ar Ar'(Het)
cat = Pd(PPh3)4, Pd(OAc)2/L, Pd(OAc)2, Pd-cluster
base = Na2CO3, K2CO3, Cs2CO3, KF, K3PO4, PhONa, Ba(OH)2, TlOH
solvent = DMF, toluene, benzene, THF, dioxane, DMF-H2O, PhMe-H2O, H2O
X = I, Br, Cl, OTf
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15Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 2394
B(OH)2 X+Y Z
Pd(OAc)2 or PdCl2base, H2O, rt Y Z
X: Br, I; Y: H, p-F, p-(4-n-amylcyclohexyl); Z: m-, p-OH; o-, m-, p-COOH
B(OH)2 Br+
Y: H, F
Y OH
COOH
Y OH
COOH
+
COOH
I
PhB(OH)2Pd black, NaOH
H2O, rt
COOH
Ph
N
Z+
Z: NO2, NH2, OEt
BrPhB(OH)2Pd(OAc)2, Na2CO3
DMF-H2O, 90-130oC N
ZPh
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Suzuki reaction
Metalloorg. Khim., 1989, 2, 1200
Izv. Akad. Nauk SSSR, 1989, 2394; Dokl. Akad. Nauk SSSR, 1995, 340, 775
Ph4BNa +Z base, H2O, rt
Pd(OAc)2 or PdCl2
ZPhX
HO2C BrPdCl2 (0.0004 mol%), Na2CO3
HO2C Ph
H2O, Ph4BNa+
4 HO2C Cl + Ph4BNaPdCl2, NaOH
H2O, 4 HO2C Ph
72%
X: Br, I;
Z: m-, p-OH;p-CHO;
m-, p-CO2H;
m-, p-NO2, etc.
Ph4BNa+2 Ar2IX1% PdCl2, Na2CO3
H2O, 80oC
4 ArPh
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Heck reaction
Russ. Chem. Bull., 1992, 41, 2130
+
Z ZX CO2H
PdCl2, Na2CO3
DMF:H2O, HMPA:H2O,
or neat H2O, 100oC
CO2H
J. Organomet. Chem., 1989, 371, 397
+X CO2HK2CO3, 80
oC, 2h
K2CO3, KOAc, 50oC, 1h
CO2H
HO2C HO2CPdCl2, H2O
97%
98%
X: I, Br
Z: H, p-Cl, p-MeO, p-Ac, p-NO2,
p-CHO, p-OH, m-CO2H
X: I; Pd(OAc)2, 0.005%, K2CO3, H2O, 24h, 100oC, TON = 200 000
+(m-O2NC6H4)2I+X
- Pd(OAc)2, Na2CO3
H2O, rt, 1hCO2H
CO2HO2N
X: HSO4- (97%), BF4
- (80%)
Dokl.Akad. Nauk SSSR, 1990, 313, 107
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Carbonylation
Dokl. Akad. Nauk SSSR, 1990, 312, 1129
ArIPd(OAc)2, 1 atm CO, K2CO3
DMF:H2O (2:1), 25-50oC
ArCOOH
Ar:
Z
Z: NO2, Cl, CN, Me, NH2, etc.
S
Z: m-, p-COOH; o-, m-, p-OH
Z
I
Pd(II), CO, base
H2O, 25-50oC
Z
COOH
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Carbon-heteroatom bonds
Zh. Org. Khim., 1994, 30, 876
Tetrahedron Lett., 1998, 39, 5621
R
+ (EtO)2P
H
O A or BI
R
P(O)(OEt)2
NH
NN
+ Ph2IBF4
Pd(OAc)2, K2CO3
H2O, 100oC N
NN
+
Ph
NN
NPh
A: Pd(OAc)2, TPPMS, NaOH
Bu4NCl, PhH-H2O, 60oC
B: Pd(OAc)2, TPPMS, Et3N
MeCN-H2O, rt
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Reaction in microemulsion
Reactions which can be readily run in microemulsion media at preparative scale
I
Z
COOH
Z
Ph
Z
Ar
Z
X
Z
CO (1 atm), PdCl2, K2CO3
Pd(OAc)2, Ph4BNa, KOH
Pd(OAc)2, ArB(OH)2, KOH
Pd(OAc)2, CH2=CHX, K2CO3
Z: Alk, NO2, OR, COOR, CN, Hal, etc.; X = COOR, Ar, 4-PyMicroemulsion media: surfactant (anionic, cationic, ornon-ionic) – co-surfactant (alkanol C2-C5, or alkyl ethers of mono or diethyleneglycol) – water (molar ratio 1:5-6:200)
Surfactant C17H33CO2K
PdCl2 (0.01 mol%), Yield 90%Heck reaction
TEM view of
Pd nanoparticles
oil water
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1 Qualitative measure of sol stability in the reaction mixture. +++ the
sol rapidly forms and shows no signs of degradation during the
reaction; ++ the sol is formed readily but shows partial aggregation
and sedimentation; + the sol is formed but readily undergoes
sedimentation; - the sol is altogether not formed 2 Palladium sol freshly prepared in the same microemulsion3 Same sol aged for 3 months4 Same sol aged for 1 year
The correlation of perfomance of microemulsion media (surfactant - n-butanol -water) in Heck arylation with the stability of palladium sol in the same system
Surfactant Catalyst (mol %) Time, h Yield, % Sol stability 1
C17H33COOK PdCl2 (0.01) 8 90 +++
C15H31COOK PdCl2 (0.01) 8 78 +++
C13H27COOK PdCl2 (0.1) 8 32 ++
C11H23COOK PdCl2 (0.1) 8 10 +
C16H33NMe3Br PdCl2 (0.01) 8 86 +++
C16H33SO3K PdCl2 (0.1) 8 4 -
C17H33COOK Pd2 (0.1) 3 40 +++
C17H33COOK Pd3 (0.1) 3 47 +++
C17H33COOK Pd4 (0.1) 3 39 +++ TEM view of
Pd nanoparticles
oil water
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I.P. Beletskaya"Palladium-catalyzed Organic Reactions in Aqueus Media."In: New Aspects of Organic Chemistry II.Organic Synthesis for Material and Life Sciences, 1992, 31.
I.P. Beletskaya, A.V. Cheprakov"Aqueous transition-metal catalysis."In: Organic Synthesis in Water.Ed. by P.A. Grieco, 1998, 141.
I.P. Beletskaya, A.V. Cheprakov"Aqueus Palladium Catalysis."In: Handbook of Organopalladium Chemistry for Organic Synthesis.Ed. by E. Negishi, 2002, Vol. 2, 2957.
I.P. Beletskaya, A.V. Cheprakov"Palladium (0)-catalysed Reactions in Aqueous Medium and Synthetic Applications"In: Transition Metal Catalysed Reactions.Ed. by S.-I. Murahashi, S.G. Davies, 1999, 55.
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Palladium catalyst on soluble polymers
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TEM image of Pd nanoparticles
stabilized by block copolymer micelles
Formation Pd nanoparticles in block copolymer micelles
(PS-PEO - polystyrene-poly(ethylene oxide)
CPC – cetylpyridinium chloride
No change of activity
after 1 year of storage
Langmuir, 2000, 16, 3626
J. Phys. Chem. B., 2001, 105, 9077
KBH4
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Suzuki and Heck reactions in water
93% in air (96% in Ar)
4-7% of biphenyl (4-7%)
[Pd] 1 mol%
rt, KOH/H2O (10 h)C6H5B(OH)2
I
CO2H
C6H5
CO2H
+
I
OH
[Pd] 1 mol%
C6H5
OH
C6H5B(OH)2rt, KOH/H2O, Ar, 4 h
+
68% in Ar, 74% in 10 h
13-16% of biphenyl
CO2H
I
[Pd] 1 mol%
rt, KOH/H2O, 20 h
HO2C
S B(OH)2+
98%S
I
CO2H
[Pd] 1 mol%
O
O
C4H9
CO2H
O
O
C4H9+
Bu3N/H2O, 50oC, 3 d
98%
[Pd] 1 mol%
rt, KOH/H2O (20 h)C6H5B(OH)2
N
I
CO2H
N
C6H5
CO2H
+
98%
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80
85
90
95
100
1 2 3 4 5
cycle number
Catalyst recycling (ultrafiltration)
50
60
70
80
90
100
1 2 3 4 5
cycle number
in water in methanol
Convers
ion, %
[Pd] 0.3 mol%
rt, KOH/H2O, 10 h
or 50 0C, MeOH, 7 h
C6H5B(OH)2
CO2H
I
CO2H
C6H5
+
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Conversion >98%
Yield 81-85%
Catalyst recycling (centrifugation)
Suzuki-Miyaura reaction in methanol
run 1 2 3 4 5
yield, % 81 85 83 84 84
2306596878694Yield, %
55072>99>998898Conv. ,%
BrClBrIIIIX in
RC6H5X
p-Acp-NO2p-NO2p-NO2o-NO2p-CH3Om-CO2HR in
RC6H5X
[Pd] 1 mol%
rt, KOH/MeOH, 20 hC6H5B(OH)2+
X
R
Ph
R
I
[Pd] 1 mol%
KOH/MeOH, rt, 20 hC6H5B(OH)2+
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before (A) and after Suzuki-Miyaura reaction (B for liquid phase, C for deposited phase)
and after interaction of the catalyst with m-iodobenzoic acid in the presence of KOH (D)
1.7 nm 1.9 nm
2.4-3.1 nm
Agglomerates
(2.6-7.2 nm)
of particles
(0.6-0.8 nm)
TEM images of the PdNPs
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ArX + 2OH-
ArX+Ar'B(OH)2
+ 2OH-
ArPdX(OH)22-
ArPdAr'(OH)22-
ArAr' +2OH-
Ostwald ripening of PdNPs
Synlett, 2008, 1547
micelle
Pd
Pd
micelle
Pd
in the presence of ArX and in Suzuki-Miyaura reaction
micelle
Pd
Pd
Pd
Pd
Pd
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Heck reaction
''Pd'': PdCl2 + PVI or PVI-PVC
PVI: poly(N-vinylimidazole)
PVI-PVC: co-poly(N-vinylimidazole-
N-vinylcaprolactam)
Run 1 2 3 4 5
Yield, % 99 99 91 94 98 ( PdCl2 : PVI-PVC=1:5)
97 99 96 92 92 ( PdCl2 : PVI-PVC=1:10)
I
OC4H9
O
OC4H9
O
+2 eq K2CO3
DMF, 100-120oC
1 mol% ''Pd''
N
N
N O
n m
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Reactions of n-butyl acrylate with p-acetylphenyl bromide
Run 1 2 3 4 5
Yield, % 99 99 93 92 98
by 1H NMR
TEM images of the palladium nanoparticles
J.Organomet.Chem. 2007, 692, 4402
OC4H9
O
O
BrO
C4H9
O
O
+DMF, 120°C, 2h
1 mol% ''Pd''
2 eq K2CO3
''Pd'' = PdCl2/PVI-PVC=1:5
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Novel recyclable catalyst for the cyanation of arylbromides
R: H, p-Ac, p-NO2,m-CHO, p-Me, p-OMe
0.1-1 mol % [Pd]
K4[Fe(CN)6], Na2CO3, DMF
80-97%
[Pd]: PdCl2 / poly(N-vinylimidazole-co-N-vinylcaprolactam) 1:5
120-140oC, 5-13 h
R
Br
R
CN
Br
O
CN
O5 mol% [Cu], K4[Fe(CN)6]
Na2CO3 , TBAB, DMF
140oC, 14 h
91%
[Cu]: CuI / poly(N-vinylimidazole -co-N-vinylcaprolactam) 1:5
Recycling: For R= p-Ac 5 consecutive cycles with constant yields ~93%
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Alkoxycarbonylation of aryl iodides catalyzed by
polymer-supported palladium
Entry Catalyst Base Temp, oC
Pressure ofCO, atm
Yield, %
Influence of base and catalyst1 H2PdCl4 KOH 50 1 112 H2PdCl4 K2CO3 50 1 183 H2PdCl4 Et3N 50 1 324 K2PdCl4 KOH 50 1 455 K2PdCl4 K2CO3 50 1 536 K2PdCl4 Et3N 50 1 85
Influence of CO pressure 7 K2PdCl4 Et3N 50 1 708 K2PdCl4 Et3N 50 5 489 K2PdCl4 Et3N 50 30 41
Influence of temperature10 K2PdCl4 Et3N 25 1 811 K2PdCl4 Et3N 40 1 6312 K2PdCl4 Et3N 55 1 92
1 mol % "Pd"5 mol %PVC-PVI
CO, baseMeOH
IO
O
PVI-PVC = poly(N-vinylimidazole-co-N-vinylcaprolactam)
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34
Methoxycarbonylation of aryl iodides
I
R
1 mol % K2PdCl45 mol % PVC-PVI
CO (1 atm), Et3N
MeOH
55oC, 60 h
R
O
O
Yield of RC6H4C(O)OMe, %Entry R Cycle 1 Cycle 2 Cycle 3
1 H 95 92 932 Me 92 92 903 OMe 91 89 834 C(O)Me 97 95 94
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Phosphorus
Greek ‘phosphoros’
means light bearing
Chemical phosphorus means:
1. Biological active compounds
2. Complexing agents
3. Ligands
4. Phosphorus containing polymers
5. Reagents for organic synthesis
and more ...
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36
Synthesis of arylphosphonates
N
Cl5
N
Cl4
P(O)(OH)2
N
Cl4
N
Cl
NC NC
Cl
Cl
P(O)(OH)2
ArP(O)(OR)2ArHal + (RO)3PCat.
+ ( Me3SiO)3P1) NiCl2
2) MeOH
+ ( Me3SiO)3P
or
(AlkO)3P
1) NiCl2
2) MeOH
Alk = Et, Bu
- RHal
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37
Synthesis of arylphosphonates
Z
X
Z
P(O)R2
R2P(O)H, [Pd]
R = AlkO, Ph
X = I, Br
[Pd] = Pd(OAc)2, Pd(OAc)2 + 2L
solvent free or aqueous solution (H2O or MeCN-H2O (1:1))
L = Ph3P, Fu3P, Ph2P(m-C6H4SO3Na)
70-80oC
70-100%
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38
Synthesis of vinylphosphonates
OR (NEt 2)
X
R'
R
Br
R
OR (NEt 2)
P(O)(OEt)2
R'
R R
(EtO)2P(O)
R'
OR(NEt 2)
R'
OR(NR 2)
(EtO)2P(O)H, [Pd]
or
X = Br, ClR = H, Me
or
20 - 100oC
Tetrahedron Lett., 1999, 40, 569
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39
Synthesis of arylphosphines
ArHal +Cat.
PR
R'P
R
R'
PR
H
SiMe3
PdCl2(MeCN)2
PR
H
Ar(Het)
PR
1
R2
SiMe3
PdCl2(MeCN)2
PR
1
R2
Ar(Het)
Ar (Het) X +
20 - 100oC
70 - 90%
Ar (Het) X +100oC
75 - 90%
ORO2C Br
[Pd]
ORO2C PRRP(SiMe3)2 +
100 - 120oC 2
SiMe3 Ar
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40
Synthesis of vinylphosphines
VinPPh2VinHal + Ph2PHCat.
R
R'
X
OR(NEt 2)
Ph2PH, [Pd] R
R'
PPh2
OR(NEt 2)
Ph
Br
SiMe3
Br
Ph
Br
Et
Ph
PPh2
SiMe3
PPh2
Ph
PPh2
Et
100oC
Ph2PH, [Pd]
94-95%
EtO
Br
Ph
Br
H(O)C
Br
EtO
PPh2
Ph
PPh2
H(O)C
PPh2Ph2PH, [Ni]
Et3N, DMF, 120oC
75-98%
Et3N, PhH or PhMe, rt
R = H, Me, SiMe3
R' = H, Me
[Pd] = PdCl2(PPh3)2
92-96%
Tetrahedron Lett., 1999, 40, 573
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41
Ni-catalyzed cross-coupling of terminal alkynes
with chlorophosphines
R R'2PCl
PhPCl2
PCl3
R
R
PR'2R
R
R
P Ph
R
R
P R
R = Ph, Am, t-Bu, TMS
R' = Ph, n-Bu, i-Pr, t-Bu
Cat. = Ni(acac)2, Ni(PPh3)2Br2, Ni(COD)2
Cat.
Et3N, PhMe, 80oC, 10 min
+
+
+
87-99%
~99%
~99%
Org. Lett, 5, 4309, 2003
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42
Cu-catalyzed cross-coupling of terminal alkynes
with chlorophosphines
R R'nPCl3-n
CuX (1 mol%)PR'nR
S N
Ph2PCl, i-Pr2PCl, t-Bu2PCl, (i-PrO)2PCl, (Et2N)2PCl, PhPCl2, PCl3,
OPCl
O
+
Et3N, MePh, r.t., 6-8 h3-n
R = Pr, Am, 4-MeOC6H4, 4-Me2NC6H4, 3-CF3C6H4, MeOCH2, Me2NCH2, 2-Py, ,
R'nPCl3-n:
Synthesis, 2835, 2003
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43
Hydrogenation of vinylphosphonic acids
P(OH)2
Ar
O
P(OH)2
Ar
O
*H2 (10 bar), (P*P)RuBr2 (1 mol%)
MeOH, 80oC, 100% conv.
Ar: Ph, 4-MeC6H4, 4-ClC6H4, 1-Naphtyl
77-86% ee
Tetrahedron Asymmetry, 12, 319, 2001
PPh2
PPh2
MeO
MeO
PPh2
PPh2
MeO
MeO
P
P
P
P
O
O
(S)-BINAP
2
2
(P*P):
(R)-MeO-BIPHEP (R)-2-furyl-MeO-BIPHEP (R,R)-Me-DuPHOS
48-82%
R + HP(O)(OEt)2(EtO)2P
R
O
Pd2(dba)3/PPh3 or Pd(PPh3)4 (3 mol%)
THF,
Hydrophosphorylation of alkynes
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44
95% ee
P(O)(OEt)2
MeO
reveals anti-dopaminergic activitywithout extrapyramidal side effect
88% ee
P(O)(OEt)2
Ar = Ph, 4-BuiC6H4, 4-PhC6H4, 1-Naphtyl, 2-Naphtyl, 6-MeO-2-Naphtyl
88-95% ee
(EtO)2P
Ar
O
(EtO)2P
Ar
O
H2 (5 bar), [Ir(cod)L*]+ [BArF]- (1 mol%)
CH2Cl2, 40oC, 100% conv.
[Ir(cod)L*]+ [BArF]- =
CF3
CF3
B
4
-
P(o-Tol)2Ir
N
O
t-Bu
+
Hydrogenation of vinylphosphonates
Tetrahedron Asymmetry, 14, 1397, 2003
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45
X
R P(OEt)2
O
NHPMP
R P(OEt)2
O
*
OH
R P(OEt)2
O
CH3
R P(OEt)2
O
Pd(OCOCF3)2/(R)-MeO-BIPHEP
1 atm., TFE, 80oC
R: Ph, 4-FC6H4, 4-MeOC6H4, 4-MeC6H4, 2-MeC6H4, 1-Ad, Me
up to 55% ee
[Rh(COD)2]+SbF6
-/(R)-BINAP
10 atm., MeOH, 60oC
R: Ph, 4-FC6H4, 4-MeC6H4, 2-thienyl
up to 94% ee
[Ir(COD)L]+[BArF]
-
5 atm., CH2Cl2, 40oC
R: Ph, 4-PhC6H4, 1-Np, 2-Np, 2-(6-MeO-naphthyl)
up to 94% ee
H2
X = NPMP, O, CH2
-Amino and -oxy phosphonic acids
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46
P(O)(OR)2Ar P(O)(OR)2Ar
HCOONH4 (6 equiv.), 5 or 10%Pd/C (3 mol%)
H2O, , 2-10 h
R = H, Et
Ar = Ph, 4-MeC6H4, 4-BuiC6H4, 4-PhC6H4, 4-MeOC6H4,
1-Nf, 2-Np, 6-MeO-2-naphthyl, 3-Py, 3-Quinolyl, 6-Quinolyl
Isolated yield 70-90%
Reduction of -arylethylphosphonic acids and esters by
palladium catalysts on solid supports
Hydrogen Transfer Reduction:
Russ. J. Org. Chem. 2002, 38, 537
Ar = Ph, R = H; HCOOH (4 equiv.), PdCl2/Al2O3 (10 mol%), 2.5M NaOHaq, , 1 h: Cycles Yield, %
1 1002 1003 984 945 90
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47
P(O)(OH)2Ph P(O)(OH)2Ph
H2 (1bar), [SiO2-GluCs-Pd] (3 mol%)
H2O, , 1h
Cycles Yield, %1 811 1002 1003 1004 985 99
O
CH2OH
NH2
OHO
CH2OH
NH2
OH O
PdCl2
O
O
CH2OH
N
OH OO
N
CH2OH
OOH
SiO2
n
n
palladium(II) complex immobilized to glutaraldehyde-crosslinked silica-supported chitosan
[SiO2-GluCS-Pd]:
or: H2 (1 bar), 10%Pd/C(en) (3 mol%), H2O, , 1h: Cycles Yield, %
1 1002 1003 1004 1005 100
Russ. J. Org. Chem. 2006, 42, 990
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48
R
R
PPh2
R
Ph2P
R
Ph2P
PhH, 80oC or MeCN, 130
oC
R = Ph, n-Pr, n-Am, t-Bu,
CH2OCH3, CH2N(CH3)2
+ Ph2PHPd(0) or Ni(0) Pd
2+ or Ni
2+
Pd(0) or Ni(0), H+
-isomer-isomer
-isomer
Hydrophosphination of alkynes
Synlett, 497, 2004
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49
R1,R2 = c-C6H11, c-C5H10, 1-Ad;
R1 = i-Pr, R2 = i-Pr;
R1 = Ph, R2 = Ph, Me;
R1= Me, R2= -Np, , ;
Z = c-C6H11, t-Bu, Bn.
NZ
R1
R2
EtO
P
O
HEtO
EtO
P
EtO
O
C
R1
R2
NHZ
CdI2
w+
EtO
P
O
HEtO
EtO
P
EtO
O
C
R1
R2
NHZ
CdI2
w
R1
C
R2
O ++ H2NZ
O
R1=Et, Pr, Ph; R2 =H.
Z = t-Bu, Ph, Ph(CH3)CH, c-C6H11
R1,R2 = c-C6H11, c-C5H10, Pr
Z = Ph(CH3)CH, c-C6H11
S
SynLett, 9, 1393, 2005
Russ. J. Org. Chem., 517, 2005
Synthesis of -aminophosphonates and
-aminophosphonic acids
(t = 45-90 sec., yield: 89-95%)
(t = 1,5 – 10 min., yield: 86-94 %)
(t = 10-25 min., yield: 72-92%)
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50
O
O
EtO
P
O
HEtO
w
ClCH2CH2Cl
O
NHZP(O)(OEt)2
+ ZNH2+
24 min
~ 80%
(isolated yield)Z = Bn, t-Bu, Ph
N HN
NH N
MeOOC COOMe
O
H
N HN
NH N
MeOOC COOMe
O
HN HN
NH N
MeOOC COOMe
OH H
O
N HN
NH N
MeOOC COOMe
HO
O
H
N HN
NH N
MeOOC COOMe
O
O
Me
Me
12-18 min;
82-85%
(isolated yield)
-Aminophosphorylation of natural products
Synlett, 2193, 2003
Russ. Chem. Bull., 54, 262, 2005
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Sulfur and Selenium
The Sanskrit ‘sulvere’ and the Latin
‘sulphurium’ both mean sulfur
Greek ‘selene’ means moon
Chemical sulfur and selenium mean:
1. Biological active compounds
2. Semiconductors and solar cells
3. Optical materials
4. Reagents for organic synthesis
and more ...
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52
Transition metal catalyzed synthesis of diaryl selenides
ArSeAr’
Tetrahedron Lett., 2003, 44, 7039
J. Organomet. Chem., 2000, 605, 96
X = Ac
Pd(PPh3)4, Toluene 1.5 % 87 %
Pd(PPh3)2Cl2 1.5 % 93 %
Ni(bpy)2Br2 10 % 91 %
Cu(phen)I 10 % 99 %
R
Se
XX
I
R
Se SnBu3
Bu3SnI(PPh3)2PdCl2
R = H, F
+DMF, 100C
5 h
+
83-95 %
X = H, Br, CH3O, NO2, CO2Et, CH3CO
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Nickel catalyzed synthesis of diaryl selenides ArSeAr’
J. Organomet. Chem., 2000, 605, 96
Ni(PPh3)2Cl2Se SnBu3 OTf Se
+nBuOH, 100° C
LiBr, 12 h
Pd(PPh3)4, Toluene 1.5 % 0 %
Pd(PPh3)2Cl2, LiBr 1.5 % 60 %
Ni(PPh3)2Cl2 1.5 % 26 %
Ni(PPh3)2Cl2, LiBr 1.5 % 80 %
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Copper catalyzed synthesis of diaryl selenides ArSeAr’
+ Bu3SnBr
(PPh3)Cu(phen)ISeSnBu3
F
SeAr(Het)
F
+ Ar(Het)Br
DMF, 110o C
4-27 h85-94 %
[Cat]
4-CF3C6H4SeC6H4F-4
(Bu3Sn)2Se
4-FC6H4SeSnBu3 + 4-CF3C6H4BrDMF, 110
o C
Bu3SnBr
+ +
(4-FC6H4)2Se+
Pd(PPh3)4, Toluene
(bpy)2NiBr2
(PPh3)Cu(phen)I
5%
10%
10%
0%
52%
97%
45%
18%
0%
N
Br Se
F N
SeSe
F F
SSe Se
FF Se Se
Se
F
FF
65%
83%
88%
67%
Tetrahedron Lett., 44, 7039, 2003
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DMF, 110° C
10% (phen)CuI
Cl
SeNa Br
Ac
Se
AcCl
+
without additives 91% (26 h)
Bu3SnCl (10% mol) 93% (8 h)
microwave irrad. 92% (15 min)
Microwave, 300 W Heating, 110° C
ArBr ArSeAr’
t, min Isolated yield, % t, h Isolated yield, %
Br
Ac
Se
Ac Cl
15 92 8 93
Br
Me2N
Se
Me2N Cl
25 87 14 72
Br
H2N Me
Se
H2N Me Cl
25 65 18 41
N BrBr N SeSe
ClCl
20 90 7 85
N BrBr N Se
Cl
Br15 85 5 68
S
BrS
Se
Cl15 88 5 81
N
NN
BrN
NN
Se
Cl50 48 30
<15
(GC yield)
Copper(I) catalysed arylselenation of aryl bromides
R3SnCl co-catalysis. Microwave vs thermal activation
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Hal = I, R=Ac
Hal = I, R=Ac
Hal = I, R=Me
Hal = I, R=Me
Hal = Br, R=CN
Hal = Br, R=CN
40
50
60
70
80
90
100
1 2 3 4
Copper(I) catalysed arylselenation of aryl bromides.
Catalyst recycling
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R
EAr
R
ArE EAr
R
EAr
ArE
R
R
R
EAr
ArE
RR
EAr
R
R
R
ArE
Products of E-E and E-H bonds addition to alkynes
Chem. Rev., 106, 2320, 2006
J. Organomet. Chem., 687, 451, 2003
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Pd
ArE
ArE EAr
R3P
Pd
ArE
EAr
Pd
EAr
PR3n
Pd
EAr
R3P EAr
R3P
Pd
EAr
ArE PR3
R3P
Pd
ArE
R3P EAr
ArE
Pd
EAr
PR3
Pd
ArE
ArE EAr
R3P
Pd
EAr
PR3
-PR3
-PR3PR3
-PR3PR3
KPd(PPh3)4-Cl
-PdCl2(PPh3)2ArE-EAr+
+
+
cis-
cis- trans-
trans-102.7 ppm 110.5 ppm
98.8 ppm101.2 ppm
insoluble
+ ArE-
Oxidative addition and substitution reactions
Organometallics, 2005, 24, 1414
K=0.0660.007 M
at 30oC
+-
31P NMR
E=S, Ar=Ph, PR3=P(Oi-Pr)3
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59
R
PdL4
PdL2
ArE-EAr
oxidative
addition
coordinationinsertion
reductive
elimination
EAr
L2PdII
EAr
R
-LArE
PdIIL
EArL
L2PdII
EAr
EAr
R
EAr
R
ArE
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Catalytic reaction under solvent free conditions
R
EAr
R
ArE
[Pd]
ArE-EAr
Z/E > 99/1
E=S, Se
+0.3 eq. PPh3 80-120
oC
meltsolvent-free
alkyne solution in the Ar2E2/PPh3 melt i
95-99%
Polymer-supported recyclable catalyst
Org.Biomol.Chem., 2004, 2, 284
Synlett, 2005, 1015; Russ.Chem.Bull., 2004, 53, 561
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Addition reactions of Alk-EE-Alk (E = S, Se)
R + Alk2E2
Ni(acac)2/PMe2Ph (30 mol%)
neat, 100oC, 2h
AlkE
R
EAlk
Alk: Bu, Me, i-Pr, Cy
R: Bn, Ph, CH2OMe,
CH2NMe2, CMe2OH
R + Bu2S2
Pd2(dba)3/PCy2Ph (45 mol%)
neat, 140oC, 12h
BuS
R
SBu
R: Bu, SiMe3, CH2NMe2
OH
70 - 85%
83 - 89%
(~60% E = Se)
Chem. Eur. J., 2008, 14, 2420
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R
RArE ArE
R
R
EAr
EArR'EAr
R' EAr
R
ArE
+ArE-H
60-80%, E/Z ~ 1/1E=S, Se
+hv (base)
Cat.
R: CH2R'
+ +
Addition of S-H and Se-H bonds to alkynes
Ogawa, A.; Ikeda, T.; Kimura, K.; Hirao, T. J.Am.Chem.Soc., 1999, 121, 5108
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63
Ni-catalyzed S-H and Se-H bonds addition
[Ni]R R' ArEH
R
EAr
R' R'
EAr
R
+20-40
oC,
~1-3 h70-95%
+
[Ni]R ArEH
R
EAr
+20-40
oC,
~20-30 min70-95%
The catalyst from Pd(OAc)2
precursor
The catalyst from Ni(acac)2
precursor
Eur. J. Org. Chem., 2007, 3431
Organometallics, 2006, 25, 1970
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R
ArEH
acacH
Ni(acac)2
ArE
NiEAr
NiArE
ArE
n
ArE
NiEAr
NiArE
n
R
ArE
ArEH
EAr
R
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65
Relative activity of the self-organized catalysts
0
10
20
30
40
50
60
70
80
0 1 2 3 4 5 6 7
Particle size, μm
Yield, %
Organometallics, 2007, 26, 740
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66
OH
nBu
NMe2
SCy
OH
SCy
nBu
SCy
NMe2
99 (92) >99:1
98 (75) 95:5
96 (87) 91:9
Ph
OH
NMe2
SCy
Ph
SBn
OH
SBn
NMe2
98 (77) 84:16
88 (74) >99:1
68 (57) 97:3
R
SAlk
R
+5% Pd(OAc)2AlkSH
w
Alkyne Product Yield, % Selectivity Alkyne Product Yield, % Selectivity
Pd-catalyzed AlkSH addition
J. Am. Chem. Soc.,2007, 129, 7252
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C-N bond formation
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68
Beginning of the era of the catalytic aryl halides amination
Br
R
Bu3SnNEt2
NEt2
R
+
PdCl2(P(o-Tol)3)2
Kosugi, Kamayama, Migita, 1983
I
R
Ph2NH
NPh2
R
+Pd(OAc)2, CuI
H2O, BuOH, CTMAB
Davydov, Beletskaya, 1995
X
R
NR'R''
R
+ R'R''NH
Pd(dppf)Cl2 orPd(BINAP)Cl2
tBuONa, dioxane
Buchwald, Hartwig, 1995
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69
Arylation of benzotriazole
SO
O
O Na
P
O
N
N
I
O
IS
Br
N
BrN
O
O-
3
tppts =
Cu2+
Cu(II) =
HetHal =
Ar(Het)
NN
N
H
NN
N
Ar(Het)Hal
PdCl2L2 (2%)
K2CO3/CetMe3Br
Cu(II) (2%)
DMF, 100oC
+
79-96%
Ar
NN
N
H
NN
N
Pd(OAc)2 (2%)
2 tppts, NaOH
Cu(II) (2%)
H2O, 100oC
+
90-95%
2 2Ar2I+BF4
-
Ar
NN
N
H
NN
N
Pd(OAc)2 (2%)
2 tppts, NaOH
H2O, 100oC
+
90-95%
Ar2I+BF4
-N Ar
N
N
+
Ar(Het)
NN
N
H
NN
N
Ar(Het)Hal
PdCl2L2 (2%)
K2CO3/CetMe3Br
DMF, 100oC
+
79-96%
N Ar(Het) N
N
+
Ar: Ph, p-MeC6H4, p-MeOC6H4,
p-ClC6H4
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70
Arylation of tetrazoles
Tetrahedron Lett., 2002, 43, 6217
Tetrahedron Lett., 2002, 43, 6221
NNH
N
N
R
Ar2I+BF4
-N
NN
NR
Ar
NN
N
N
R
Ar++
t-BuONa, t-BuOH
80oC, 8h
~ 1.5:1
42 - 52%
NNH
N
N
R
Ar2I+BF4
-+ N
NN
NR
Ar
92 - 98%
Pd(dba)2(rac-BINAP) (2%)
Cu(II) (2%), rac-BINAP (2%)
t-BuONa, t-BuOH, 80oC, 8h
Ar: Ph, p-MeC6H4, p-MeOC6H4, p-ClC6H4
R: Ph, p-MeC6H4, p-BrC6H4, p-MeOC6H4, 4-Py
Ph
CO2
2
Cu2+Cu(II):
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71
Br
R
H2NHN
OR
HN
HN
R(H)
OH(Ph)+
Pd2dba3, L
Cs2CO3, dioxane,
100°C
OPPh2PPh2
CF3
CF3
OPAr2PAr2
62-98%
64-92%L =
L =
Ar =
Arylation of urea
Tetrahedron Lett., 2001, 42, 4381
Tetrahedron Lett., 2003, 44, 4791
R: p-CN, p-CF3, p-NO2
p-PhC(O), p-CO2Et
R: o-, p-Cl o-, m-, p-Me, o-MeO
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72
N
N
N
MeO
N
CO2Et
N
NR1
O
N
R2
R1 N N
O
N
N
NHPri
Me
Me
R2
R
R= Me, Bn
= ; ; ;
Pd2dba3, 2-[di(t-butyl)phosphino]biphenyl, toluene, t -BuONa, 100°C
Palladium-catalyzed amination and amidation of
bromoindoles and their derivatives
Amination of bromoindoles and bromotetrahydrocarbazolones
NN
NN
ON
N
NN
HN
O
Pd2dba3, Xantphos, dioxane, Cs2CO3, 100°C.
Amidation of bromotetrahydropyrazinocarbazole
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73
O
NO
N
R1
R2
N
O
R1
R2N
O
O
NH
O
NH
NO
NN
ON
O
R R
X
MeO
HN
CO2Et
O
N
Me
CO2Et
NN
ON
Me
EtO2C
Me Me
N
Me
CO2Et
HN
HN
ON
Me
EtO2C
Me Me
R
= ; ;
R= Me, BnX = O, NMe
Pd2dba3, Xantphos, dioxane, Cs2CO3, 100°C.
Amidation of bromoindoles and bromotetrahydrocarbazolones
Possible biological activity: Antidepressant, Psychotropic, Anxiolytic, Psychosexual disfunction treatment
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74
Solvent-free amination
Br Z
O
N
OO
O
N CF3F3C
O
NH
NH
ZZ
O
H2N NH2
O
H2N
O
HN
Z
NH2
PhS
O2N
PhS NO2
NH
F3C
NH2
NH
CN
Z = CN, CF3
Reaction conditions:
100oC, graphite,
Base: Cs2CO3 or t-BuONa
[Pd]: Pd2(dba)2, Pd(OAc)2
L: Xantphos, DPEPhos
diaza-18-crown-6
60%, 10 h
72%, 4 h70%, 3 h70%, 8 h
Z = CF3, 75%, 5 hZ = CN, 65%, 6 h
Mendeleev Commun., 2003, 4, 13
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75
Hal
H2N NH
NH2
H2N NH
NH R
NH
NH
NH RR
N NH
NRR
R R
H2N NH
NH
NH
NH
NH2
R
Hal = Cl, Br, I
n nx
n = 0, 1; x = 0, 1, 2, 3, 4
+
n nx
n nx
n nx
n nx
n nx
R = Hal1
Mono-, di-, and polyarylation of linear polyamines
Tetrahedron Lett., 1997, 38, 2287
Synlett, 1999, 1459; Eur. J. Org. Chem., 2005, 261
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76
Z
H2N X NH2
Hal1
Hal2
HN X
NH
NHN NH
X
NH2N X NH
NH
X NH2
NHN NH
X
HN
X
NHN
Hal1, Hal
2 = Cl, Br
n nm
n = 0, 1; m = 1, 2, 3, 4
+
X = NH, O
Z = CH, N
n
n
m
n nm
n nm
n nm
n n
n n
Amination of dihalobenzenes and dihalopyridines with
polyamines
Tetrahedron Lett., 2008, 49, 3950
Tetrahedron Lett., 2003, 44, 1433
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77
A new family of polyazamacrocycles
N
HN
NH
X
N
HN
NH
X
HN
NH
X
HNHN
X
Z
Z
HN
NH
X
Z
Z
NH HN
X
Synlett, 2005, 87; Chem. Lett., 2005, 110
Tetrahedron Lett., 2006, 47, 2691; 2001, 42, 4983, 4987; 2003, 44, 1433
Z
Z
Cl Cl
Z = CH, CO
Z
Z
Cl
Cl
Hal
Hal
Hal
Hal
Hal = Cl, Br
NHal Hal
N
Hal Hal
X NH2H2N
Pd(dba)2/BINAP 4-8 / 4.5-9 mol%
t-BuONa or Cs2CO3
dioxane, 6 - 72 h
+
X: NH(CH2)2NH, NH(CH2)3NH, CH2NH(CH2)2NHCH2,
CH2NH(CH2)3NHCH2, NH[(CH2)2NH]2, NH[(CH2)2NH]3,
O(CH2)2O, CH2O[(CH2)2O]2CH2, CH2O(CH2)4OCH2
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78
OCl
ClOO
NH
HN
O
OO
NH2
O O
H2N
[Pd]
30%
+
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79
Ar X NH2NHX HNH2N
Ar HalArHal X NHHN
X
NH
HN
X
NH
NH
X HNNH
Ar
ArAr
+
Pd(dba)2/BINAP
t-BuONa or Cs2CO3
cyclotrimers
Ar HalArHal X NHHN
X NH2H2N
X
NH
NH
X
HN
HN
Ar
Ar
+Pd(dba)2/BINAP
t-BuONa or Cs2CO3
cyclodimers
Helv. Chim. Acta, 2005, 88, 1983
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80
Z
Z
Cl
Cl
H2N X NH2Z
Z
NHNH
X
Z
Z
HNHN
X
X
HN
HN Z
Z
Z
Z
Z
Z
Z
Z
NHNH
X
HN
NH X HN
HN
X
Z = CH, CO
n nm
n = 0, 1; m = 2, 3, 4
X = NH, O
+
nn
m
n
nn
n
n
n
n
n
n n
Intramolecular amination of dichloroanthracenes and
anthraquinones
Helv. Chim. Acta, 2005, 88, 1983
Eur. J. Org. Chem., 2005, 281; Tetrahedron Lett., 2001, 42, 4983
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81
O
O
Br
Br
H
HN
O
BrH
OX
NH
O
OBr
H
XNH2H2NH
H
H
HH
HH
HH
B
0.5 equiv.
O
O
NH
HN
X NH2
X
H2NH
O
Br
Br
HO
X NH2H2N
2.5-3 equiv.
HH
HHHH
A
O
O
NH
HN
X
H
O
Br
Br
HO
X NH2H2N
Pd(dba)2/BINAP 8/9 mol%tBuONa, dioxane reflux
HH
HHHH
1 equiv.
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82
O
NH
NH
HO X
HN
O
O
HN
H
X
NH2 NH2
X
O
NH NH
H
O
O
H
O
NH
NH
X
X
H
H
HH
H H
H
HH
H
HH
+
or
B
A
+
O
Br
Br
HO
H
HH
Chem. – Eur. J., 2005, 11, 1730
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83
Mono-, bis- and triscyclen structures with polyamine linkersX
NH2NH2
NH N
N HN
Br
Br
NH N
N HN HN
HN
X
XHN
HN
NH N
N HN
N HN
NH N
Br Br
[Pd]
[Pd]
[Pd]
Y
NH
NH HN
N
N
NH
HN
NH
NH
X
N
N
HN
H2N X NH2NH2YH2N
+
1 equiv.
X = CH2NH(CH2)2NHCH2,
X = CH2NH(CH2)3NHCH2,
X = CH2O(CH2)2O(CH2)2OCH2,
X = CH2O(CH2)2OCH2,
X = CH2,
cyclodimer
X = Y = O(CH2)2O,
X = CH2O(CH2)2OCH2
Y = CH2
40%
36%
65%
69%
61%
37%
38%
NHN
NHN
NH
X
NH
N
N
N
N
HNN
NNH
HN
X
HN
Br Br
+
Tetrahedron Lett., 2008, 49, 3950
X = CH2O(CH2)2OCH2,X = CH2,
54%
15%
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84
Acknowledgements
Afanas'ev V.V.
Ananikov V.P.
Artamkina G.A.
Averin A.D.
Bessmertnykh A.G.
Cheprakov A.V.
Davydov D.V.
Ganina O.G.
Goulioukina N.S.
Kabachnik M.M.
Prof. Guilard R.
Prof. Genet J-P.
Prof. Pfaltz A.
Financial support: INTAS, RFBR, CRDF, President grant for Leading School
Cooperation:Kashin A.N.
Kazankova M.A.
Latyshev G.V.
Lukashev N.V.
Orlov N.V.
Ranyuk E.R.
Shukhaev A.V.
Shulyupin M.O.
Sigeev A.S.
Titanyuk I.D.
Zobnina E.V.