COORDINATION CHEMISTRY AT CARBON
COORDINATION CHEMISTRY AT CARBON
A. F. with M. Alcarazo, C. W. Lehmann, A. Anoop, W. Thiel, Nature Chemistry 2009, 1, 295
Cl2
Cl1
C16
C15
C17
Au2
Au1
Cl4
C14
C25
C18
C3
C13
C4
C1
O1
Cl3
P4
C2
C20
C19
C7
C21
O2
C8
C12C9
C11
C5
C24
C10
C22
C23
C6
F2
F1
F4Sb1F5
F6
F3
C7
C6
N2
C10
C9
C5
C2
C23N4
C3
C1
N3
N1
C22
C24C11
C8
Au1
C21
C25
C4
C26
P1
C46
C31
C41
C36
C32
C45
C35
C33
C42
C34
C44
C43
A. Fürstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 3210
for a large scale synthesis of tetrakis(dimethylamino)allene, see:
A. Fürstner, M. Alcarazo, H. Krause, Org. Synth. 2009, 86, 298
C25
C24
C26
C23
C21
C22
C35
C34
C36
C33
C31
C32
P1
C12
C11
C13
Au1
C14
C16
C8
C4
C15
N3
C5
C2
N6
C1
C7
ENDIAMINE LIGANDS
A. Fürstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 3210
C12
C8 C7
N1C2
C1
C9
C4
C3
C6
N2
C5
O1
C13
C10 C11
C43
C44
C42
C45
C35
C36
C3
C41
C46
C34
C2
C5
N2
C31
P1
C33
N1
C1
C32
Au1
C26
C4C21
C6
F3
O1
C25
C7
F4
C22
F2
C24
Sb1
C23
C11
F5
C12
C16
F1
F6
C13
C15
C14
ENDIAMINE LIGANDS
A. Fürstner, M. Alcarazo, R. Goddard, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 3210
UPREGULATION OF THE ACCEPTOR PROPERTIES OF NHC‘S
A. F. with M. Alcarazo, T,. Stork, A,. Anoop, W. Thiel, Angew. Chem. Int. Ed. 2010, 49, 2542;
for the cyclophanic NHC‘s see: A. F. with M. Alcarazo, H. Krause, C. W. Lehmann, J. Am. Chem. Soc. 2007, 129, 12676
N NO
N
CN
O
NMe2O
N
CNmCPBA Me2NC(O)Cl
TMSCN
76% 54%
A. Pfaltz, F. Vögtle et al.
Synthesis 1999, 597
CYCLOPHANIC NHC’S
A. F. with M. Alcarazo, H. Krause, C. W. Lehmann, J. Am. Chem. Soc. 2007, 129, 12676
1980 cm-1
NN MesMes
NN PhPh
N N
N
Ph
Ph
PhN
MeN
Me
19902000
ν
CYCLOPHANIC NHC’S
J. Am. Chem. Soc. 2007, 129, 12676
Stable carbenes other than NHC‘s:
AMINO-YLID CARBENES (AYC‘s)
AMINO-YLID CARBENES (AYC‘s)
A. F. with M. Alcarazo, K. Radkowski, C. W. Lehmann, Angew. Chem. Int. Ed. 2008, 47, 8302
C8
C2N1
C18B
C3C18A
C11C1
C17
C4
C12
Rh1
C16
C13B
C5
C13A
C6
I1
N2
C15
C14
C7
CARBENES STABILIZED BY LATERAL ENAMINES
A. F. with M. Alcarazo, K. Radkowski, R. Goddard, Chem. Commun. 2011, 776
C24
C34
C35
C25
C23
C36C33
C26
C22
C32
C21
C31
P1
C14
C1
C3
C13
C12
C2
Au1
C4
C41 C8
C7
C11
C5
C6
C9
C10
Cl1
C42
C46C43
C45
C44A. F. with M. Alcarazo, R. M. Suarez, R. Goddard,
Chem. Eur. J. 2010, 16, 9746
PUSH-PULL HETEROCUMULENES HAVE CARBENE CHARACTER
PREPARATION OF IMIDAZOLIUM SALTS WITH
PREVIOUSLY INACCESSIBLE PATTERNS
N NR1 R2
X
N NR1 R2
A
B
N NR1
R2X
C
N ZR1
X
R2NH2
Y
NR1
O
O
R3
R4
R3 R4
R3 R4 R3 R4R3 R4
HO
OR4
R3
R1NH2
F
HX
E (Z = O)
D (Z = NR2)
A. F. with M. Alcarazo, V. César, C. W. Lehmann, Chem. Commun. 2006, 2176
Org. Synth. 2008, 85, 34
PREPARATION OF IMIDAZOLIUM SALTS WITH
PREVIOUSLY INACCESSIBLE PATTERNS
N N
X
N N
ClO4
PhN N
ClO4
BF4
NNPh N N
ClO4
75% (X = BF4)
91% (X = ClO4)
64% 91%
59% 88%
N
N
BF4
OMe
83%
NN
BF4 61%
N N
MeO
BF4
69%
O3
C15
O4
O1
Cl1
C13
C14
C6
O2
C5
C7
C24
C4C1
C8
C21
C20
N1
C9
N2C16
C19
C23
C2
C12
C3
C17C18
C10
C22 C11
A. Fürstner, M. Alcarazo, V. César, C. W.
Lehmann, Chem. Commun. 2006, 2176
METAL-NHC COMPLEXES BY OXIDATIVE ADDITION
N N
Cl X
N N
Pd ClPh3P
XPd(PPh3)4
2 PPh3
1 a-ccis-2a-c
PPh3
N N
Pd PPh3Ph3P
X
trans-2a-c
Cl
C62
C4
C61
C41
N2
C42
C3
P2
C1
C52
C12
Pd1
C2
C51
C31
Cl1
N1
C32
C11
P1
C5
Cl2-
A. Fürstner et al., Organometallics 2003, 22, 907; Chem. Eur. J. 2005, 11, 1833
METAL-NHC COMPLEXES BY OXIDATIVE ADDITION
Pd
N SPh
Ph3P PPh3
Cl
PF6N N
NiEt3P PEt3
Cl
PF6 PF6
N N
NiPh3P PPh3
Cl
Cl
N N
Pd PPh3Ph3P
Cl
Ph
C13C14
C34
C35
C15C12
C55
C33
C36
C54
C56
C16C11
C32
C31
C53
C51C3
C4
N2
C2
C22
C52
P1N5 C1
C21
C23C5
C46C41
Pd1
C45
C26
C24
C42
C25
C44C43
Cl2Cl1
C15
Cl1
Cl2
C14
C16
C45C44
C46
Pd1
C13
C11
C43
C41
C12
C42
O5
C4
P1
N2
C1
C36
C31
C3
C35
C21
C26
C32
C34
C22
C33
C25
C23
C24
D. Kremzow, G. Seidel, C. W. Lehmann, A. Fürstner, Chem. Eur. J. 2005, 11, 1833
NEW APPLICATIONS OF
N-HETEROCYCLIC CARBENE COMPLEXES
9-R-9-BBN, KOMeR
OMe
MeOCl
OMe
MeO
cat.
Pd(OAc)2 cat.
ClN N
R = alkyl, allyl, alkynyl, cyclopropyl
A. Fürstner, A. Leitner, Synlett 2001, 290
NEW APPLICATIONS OF
N-HETEROCYCLIC CARBENE COMPLEXES
CN, NO2, CF3 etc.
X = C(O)R, COOR, CHO
ClX
O
B
OO
B
O
N NCl
cat.
Pd(OAc)2 cat, KOAc, THF O
B
O
X
1
2
A. Fürstner, G. Seidel, Org. Lett. 2002, 4, 541
anti : syn = 97 : 371%
N NCl
cat.+ PhB(OH)2
RhCl3.3H20 cat.
CHO
NO
Boc NO
Boc
OH
NEW APPLICATIONS OF
N-HETEROCYCLIC CARBENE COMPLEXES
A. Fürstner, H. Krause, Adv. Synth. Catal. 2001, 343, 343
NHC‘s CAN COEXIST WITH OLEFINIC SITES
Br
NN
NN
Ru
PCy3
Cl
Cl
PhRu
PCy3
Cl
Cl
NN
[a]
[b] [c]
2 3
4 5
Mes MesN N
Mes Mes
C21
C13 C12C22
C14
C3
C11
C4N2
C8
C7
C15
N5
C16
C1 C6
C9
C23
C10
A. Fürstner, H. Krause, L. Ackermann, C. W. Lehmann, Chem. Commun. 2001, 2240
FIRST EXAMPLE OF A METAL-SILYLENE COMPLEX
USED AS A CATALYST
N
Si
NCl
Cl N
Si
NC8K
67%Pd(PPh3)4
50%
Pd
Si
Pd
Si
PPh3Ph3P
tBu tBuN N
tBu tBuNN
O
88%
B(OH)2
+
O
Br
5 mol%
DME, K2CO3, 80°C
A. Fürstner, H. Krause, C. W. Lehmann, Chem. Commun. 2001, 2372
C22*
C21*
C4*
C8
C11*
C9
P1*
C3*
C7
C5*
C12*
C31*
C32*
N1*
N2
Pd1*
C1*
C2
Si1
Si1*
C2*
C1
Pd1
N2*
N1
C32
C31
C12
C5
C7*
C3
P1
C9*
C11
C8*
C4
C21
C22
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