Post on 17-Jul-2018
ZR
[M]+
Z
R'
Alder-ene cycloisomerization
Z
R =
Z = NTs, O
Z
R
Z
R
Z
R
Skeletal Rearrangement
ZR
R'OHOR'
Alkoxycyclization
conrotatory opening?
Metal Catalyzed Cyclization of Enynes
B. M. Trost
P. A. Wender
A. Fürstner, N. Chatani, M. Malacria, A. S. K. Hashmi, F. D. Toste, F. Gagosz, S. Kozmin, S. P. Nolan
Metal-Catalyzed Skeletal Rearrangement of Enynes: Mechanistic Pathways
MXn
RZ
Z
H
R
H
MXn
Z
R
Z
R- MXn
+
singlecleavage
doublecleavage
Z
H
- MXn
R
H
conrotatory opening
Z MXn
HR
H
- MXn
Z
R
MXn
Z
H
- MXn
R'
Metal-catalyzedAlder-enecyclosiomerization
Metal Catalyzed Cyclization of Enynes
Chem. Eur. J. 2003, 9, 2627.
TSexo
10.3
19.5O
C
C
ClC
Pt
C
Cl
C
C
C
C
CC C
C
C
C
C
Cl
C
Pt
O
Cl
C
C
CC
C
C
O
C
Pt
Cl
C
Cl
HMe
Pt
Cl
Cl
OH2
=
exo
TSendo
11.2
8.1
Cl
O
Pt
C
C
C
C
C
C
C
C
Cl
ClO
Pt
C
C
C
C
C
Cl
C
C
C
endo
Metal Catalyzed Cyclization of Enynes
MXn
Z
H
R
H
MXn
RZ
a
b
Z
HOR'
HR
Z
R
OR'
5-exo-dig
a
R'OH
R'OH
b
RZ
MXn
Z
MXn
H
H
R
H
Z
H
H
R
H
Z
H
OR'
HR
Z R
OR'
b a6-endo-dig
R'OHa
R'OH
b
Chem. Eur. J. 2003, 9, 2627
Pt(II) vs. Au(I) as Catalysts
TSexoTSendo
10.3
19.5
11.2
8.1exo
endo
Pt(L)Cl2
Pt(L)Cl2Cl2(L)Pt
Pt(L)Cl2
Cl2(L)Pt
L = H2O
PtCl2
TSexo
TSendo
0.1
exo
endo
Au
Au
PH3
Au
H3P
AuPH3
AuH3P
[Au(PH3)]+
PH3
6.2
13.4
6.1
Au(I)-Catalyzed Cyclization of Enynes: Alkoxycyclizations
Angew. Chem. Int. Ed. 2004, 43, 2402.
Ph3PAuMe, TFA
MeOH, 23°C, 30 min
(95%)
MeO2C
MeO2C
OMe
MeO2C
MeO2C
OMe
OMe
Ph3PAuMe, H3PW12O40
MeOH, 56°C, 17 h
(96%)
PhO2S
PhO2S
PhPhO2S
PhO2SOMe
Ph
HO
Ph
Ph3PAuMe, H3PW12O40
toluene, 23°C, 3 h
(100%)
O
HPh
H
Au(I)-Catalyzed Cyclization of Enynes: Skeletal Rearrangements
Angew. Chem. Int. Ed. 2004, 43, 2402.
CH2Cl2, 23°C, 10 min
MeO2C
MeO2CMeO2C
MeO2C
(96%)
CH2Cl2, 23°C, 25 min
(91%)
MeO2C
MeO2C
MeO2C
MeO2C
CH2Cl2, 23°C, 15 min
PhO2S
PhO2SPhO2S
PhO2S
Ph3PAuCl / AgSbF6
Ph3PAuCl / AgBF4
Ph3PAuCl / AgBF4
Ph3PAuCl / AgSbF6
CH2Cl2, 23°C, 5 min
(67%)
MeO2C
MeO2C
MeO2C
MeO2C OH
OH
(100%)
New Au(I) Complexes
C. Nieto-Oberhuber
N NR R'
R = R' = MesR = Mes, R' = MeR = R' = Me
Au
Cl
R = Cy, R' = HR = t-Bu, R' = HR = Cy, R' = i-Pr
P Au Cl
R R
R'
R'
R'
P Au Cl
Cy Cy
MeO
MeO
R = Cy, t-Bu
P Au NCMe
R R SbF6
New Au(I) Complexes
R = Cy, t-Bu
P Au (ArH)
RR SbF6
Angew. Chem. Int. Ed. 2006, 45, 5455.
New Au(I) Complexes
electrophilicity
AuCl
N NR R'
R = R' = MesR = Mes, R' = MeR = R' = Me
Au
Cl
/ AgSbF6R = Cy, t-Bu
P Au NCMe
R R SbF6
[Au(PPh3)(MeCN)]+SbF6-
O P3
Au Cl
/ AgSbF6
Metal-Catalyzed Skeletal Rearrangement of Enynes: Mechanistic Pathways
- [Au(PH3)] Me
single cleavage
Ea = 0.1 kcal·mol-1
!G = -0.7 kcal·mol-1
- [Au(PH3)]
Me
double cleavage
Me
H
AuH3P
B3LYP/6-31G(d), LANL2DZ (Au) (E kcal mol-1).
Au
transition state for the double rearrangement
Au
H3P
Me
H
Au
PH3
MeH
H
Me
[Au(PH3)]
Ea = 9.1 kcal·mol-1
!G = 2.7 kcal·mol-1
Angew. Chem. Int. Ed. 2005, 44, 6146.
Au(I)-Catalyzed Biscyclopropanation of Dienynes
H
CH2Cl2, 23°C, 5 min
R
R R
R
[Au(PPh3)(MeCN)]+SbF6-
R = CO2Me (98%)
R = SO2Ph (100%)
R = CH2OAc (96%)
(2 mol%)
HMeO2CCO2Me
MeO2C
MeO2C
MeO2C
MeO2C
CO2Me
CO2MeCH2Cl2, 23°C, 5 min
[Au(PPh3)(MeCN)]+SbF6-
(2 mol%)
(88%)
Chem. Eur. J. 2006, 12, 1694.
Au(I)-Catalyzed Biscyclopropanation of Dienynes
Chem. Eur. J. 2006, 12, 1694.
L-Au
L-Au
H
H
H
1.8
6.6
2.9
13.2
anti
Au(I)-Catalyzed Intermolecular Cyclopropanation
Ph
H
MeO2C
MeO2C MeO2C
MeO2C
Ph
H+
CH2Cl2, -40 to 0°C
(94%)
N NMes Mes
AuCl / AgSbF6
PhH
H
H
(77%)
PhH
H
H
(76%)
Ph
H
H
(60%, 5:1)
TsN
PhH
H
H
(75%)
TsN
PhH
H
H
(73%)
Me
H
(53%)
MeO2C MeO2C MeO2C
PhO2S
MeO2C MeO2C MeO2C
PhO2S
Angew. Chem. Int. Ed. 2006, 45, anie.200602448.
H
Au(I)-Catalyzed Intermolecular Cyclopropanation
Au(L)
R
R
R
- Au(L)+
R
(L)Au
H
H
Au(L)
R
H
H
Au(L)
RH
H
- Au(L)+
Angew. Chem. Int. Ed. 2006, 45, anie.200602448.
tBu
tBu
O P AuCl3
/ AgSbF6
-50 to 23°C
ZZ = C(CO2Me)2
Ph
Z
Ph
(67%, 3.3:1 cis/trans)
Au(I) Metallotropic Shift
Z
[AuL]Z
MeH
Z
Z
MeH
[AuL]
Me Me
[Au(L)]
[1,3]-Metallotropic shift
Angew. Chem. Int. Ed. 2006, 45, anie.200602448.
CH2Cl2, 23°C
/ AgSbF6
tBu
tBu
O P AuCl3Z
Z = C(CO2Me)2
2 : 1
Z
Z
H
Z
Me
Me
H
Z
H
Z
Me
Me
H
Me Me
+(2 mol%)
[4+2] Cycloaddition of Arylenynes
J. Am. Chem. Soc. 2005, 127, 6178-6179
Z
R1
Z
HCH2Cl2, r.t.
R1R2
R2
R3
R3[Au(L)Cl], AgSbF6
H
MeO2C
MeO2C
(86%)
H PhH
MeO2C
MeO2C
(67%)
H
MeO2C
MeO2C
(77%)
OMeH
MeO2C
MeO2C
(74%)
NO2
H
MeO2C
MeO2C
(95%)
H
MeO2C
MeO2C
(65%)
OMe
H PhH
MeO2C
MeO2C
(80%)
Ph
H PhH
MeO2C
MeO2C
(58%)
NO2
H
MeO2C
MeO2C
(73%)
Cyclopropane to Cyclobutanone Ring Expansion
Z
HH
OR
[Au(L)]
Z
H
H
[Au(L)]
OR
- [Au(L)][Au(L)]
CH2Cl2, MeOH (2 equiv)r.t., 5 min
P Au NCMet-Bu t-Bu SbF6
OR
O
H
H
E. Jiménez-Núñez, C. Claverie
R = TMS (98%)R = TBS (100%)
MeO2C
MeO2C
MeO2C
MeO2C
Cyclopropane to Cyclobutanone Ring Expansion and Prins Cyclization
CH2Cl2, r.t., 5 min
P Au NCMet-Bu t-Bu SbF6
E. Jiménez-Núñez, C. Claverie
Z
OEt
Z O
H
H
Z = C(CO2Me)2 (11%) (69%, anti/syn = 1.3:1)
Z = --- (54%, anti/syn = 3.2:1)
+ ZOEt
HH
O
O
H
H
OH
OH
O
Sulcatine G
Z
HH
OEt
[Au(L)]
PrinsZ
OEt
HH
[Au(L)]
Gold-Prins Reaction
Angew. Chem. Int. Ed. 2006, 45, 5452.
CH2Cl2, rt, 30 min
Z = C(CO2Me)2
ZO
HZ
H
O ZO
MeMe
Me
HH
+
(58%) (18%)
AuCl
Z
HMe
ClAu
O
H
AuCl
Z
H
O
Me
AuClH
Z
H
O
Me
H
AuCl
- AuCl
Gold-Prins Reaction
O
Me
Me
Me
OHH
HOMe
H
Orientalol E
CH2Cl2, rt, 30 min
AuClZO
MeZ
H
O ZO
MeMe
Me
MeMe
+
(79%) (10%)
ZO
i-PrZ
H
O ZO
MeMe
Me
i-Pri-Pr
+
(84%) (12%)
CH2Cl2, rt, 30 min
AuCl
Z
Me
O
Me
Me
[Au(L*)L']SbF6
CH2Cl2, rt, 5 min
Angew. Chem. Int. Ed. 2006, 45, 5452.
P Au NCMe
t-But-Bu SbF6
[Au(L*)L']SbF6 =
Arylation of Alkynes
AuCl3CH2Cl2, 23°C, 1 h
NH
N
R SO2Ar
R = CO2Me, Ar = 2,4-(NO2)2C6H3 30 min (75%)
R = H, Ar = Ph 24 h (55%)
N
N
O
MeO
CO2Me
Lundurine A
Angew. Chem. Int. Ed. 2006, 45, 1105.
NH
N SO2Ar
NH
NSO2Ar
CH2Cl2, 23°C
P Au NCMe
t-But-Bu SbF6
(5 mol%)R R
R = CO2Me, Ar = 2,4-(NO2)2C6H3 30 min (82%)
R = H, Ar = Ph 16 h (65%)
Arylation of Alkynes
Catelijne Amijs, Cati Ferrer
NH
N Ts
Me
Me
NH
NTstoluene, 90°C, 48 h
P Au NCMe
t-But-Bu SbF6
(5 mol%)
(58%)
NMe
O
Me
Me
NH
O
(36%)
NMe
OHMe
(27%)
toluene, 90°C, 24 h
P Au NCMe
t-But-Bu SbF6
(5 mol%)
+
MXn
RR R
R
MXn
ZR
H
Z
HOR'
RH
Au(I)
Z
H
H
R
Au(I)
Z
R
OR'
and / orR'OH
Z