Catalytic C-H Bond Activation to Organic Synthesis
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Transcript of Catalytic C-H Bond Activation to Organic Synthesis
Catalytic C-H Bond Activation to Organic Synthesis
A. Carbonylation through C-H Bond Activation
+
CO
h, 37oC, 16.5hRhCl(CO)(PMe3)2 (7mM)
(1 atm)
CHO + CH2OH
811%/Rh 103%/Rh
Sakakura, T; Tanaka, M. Chem. Lett. 1987, 249-252
A. CarbonylationB. HydroacylationC. DehydrogentionD. Orthoalkylation
RhCl(CO)(PMe3)2
h -CO
RhCl(PMe3)2
Ph Rh(PMe3)2
H
Cl
C Rh(PMe3)2
H
Cl
O
PhPh-CHO
PhH
CO
16e
14e
+
CO
h, r.t., 16.5hRhCl(CO)(PMe3)2
CH3 + CH3
CH3
+ CH3
2 % 63 % 35 %CHO OHC
OHC
Sakakura, T.; Tanaka, M. Chemistry Lett. 1987, 1113-1116
h, r.t., 16.5hRhCl(CO)(PMe3)2
CH3 CH2 CH2
H3C CH3CH2
H3C
+ +
221%/Rh 0% 0%
Sakakura, T.; Sodeyama, T.; Tokunaga, Y.; Tanaka, M. Chemistry Lett. 1987, 2211-2214
Cf. Orientation of Electrophilic Substitution Reaction in Aromatic Ring (Friedel-Craft Acylation Reaction, Vilsemeyer Formylation, etc.)
Meta-directing
Without CO, biaryl compounds are obtained.
RhCl(CO)(PMe3)2
hu -CO
RhCl(PMe3)2
Ar Rh(PMe3)2
H
Cl
Rh(PMe3)2
H
Cl
.
H Rh(PMe3)2
H
Cl
ArH Ar.
H.
ArH
Ar-Ar
H2
bond homolysis
Mechanism of Diarylation
h, r.t., 16.5hRhCl(CO)(PMe3)2
CH3CH2CO2CH3
CH3CH2CO2(CH2)3CO2CH3
2035 %/Rh
O
C (CH2)4CH3O C
O
OCH3
116 %/Rh
Sakakura, T.; Sodeyma, T.; Tanaka, M. Chem. Lett. 1988, 683-684
[Rh]
CO2[Rh]-H
CO2 [Rh]CO2CH3
CO2CH3
[Rh]-H
CO2CH3
[Rh]
H-[Rh]-H
CO2CH3
CO2(CH2)3CO2CH3
CO2CH3
H2
A
B
D
C
Dimerization of Esters
+CO2CH3
h, cat. Rh, r.t.CH=CH-CO2CH3
Sasaki, K.; Sakakura, T.; Tokunaga, Y.; Wada, K.; Tanaka, M. Chem. Lett. 1988, 685-688
Synthesis of methyl cinnamate from Benzene and methyl acrylate
[Rh]
H-[Rh]-PhH-[Rh]-H
CH
CO2CH3
Ph-CH2 [Rh]-H
PhH
CO2CH3
CO2CH3
CO2CH3
PhCO2CH3
PhCH2CH2-CO2CH3
B. Synthesis of Ketone from Aldehyde through C-H Bond Activation
O
CR H +R' M
RC
R'
O
Hydroacylation
O
CR H
R'
MR
CR'
OO
CR M H RC
M
O
R'M
R M H
C OR-H + M C O
Decarbonylation
A B
C
HRh(CO)L3 + [CH3CH2Rh(CO)L3]
Ph-COCl
C
Rh
O Ph
CO
LCl
L
CH3CH2
L2Rh(CO)Cl
+
Ph C
O
CH2CH3
Schwartz, J.; Cannon, J. B. J. Am. Chem. Soc. 1974, 96, 4721-4723
Hydroacylation was named by Schwartz.
O H
Rh(acac)(C2H4)2
C2H4, CHCl3
O+
O O
6 % 39 % 2 %
+
Lochow, C. F.; Miller, R. G. J. Am. Chem. Soc. 1976, 98, 1281-1283 Vora, K. P.; Lochow, C. F.; Miller R. G. J. Organomet. Chem. 1980, 192, 257-264
O H
RhCl(PPh3)3
r.t., CHCl3
O
Intramolecular Hydroacylation
CHO +R
R = H, CH3
RuCl2(PPh3)2
180-220oC, toluene R
O
R = H, CH3
Ar CHO + (1000 psi)(5-C9H7)Rh(2-C2H4)2
100oC Ar
O
Isnard, P.; Denise, B.; Sneeden, R. P. A. J. Organomet. Chem. 1982, 240, 285-288Marder, T. B.; Roe, D. C.; Milstein, D. Organometallics 1988, 7, 1451-1453
R CHO + R'-CH=CH-R"Ru3(CO)12, CO(12 KgCm-2)
200oC, 24-48hR', R" = alkyl or H
O
CR CH
R'
CH2-R"
O
CR CH
R"
CH2-R'+
R = Ar or amine
Kondo, T.; Tsuji, Y.; Watanabe, Y. Tetrahedron Lett. 1987, 28, 6229-6230Kondo, T.; Akazome, M.; Tsuji, Y.; Watanabe, Y. J. Org. Chem. 1990, 55, 1286-1291
<Principle of Le Chatelie>
N
C OH
+ RhCl(PPh3)3 N
C ORh
H
ClPh3P
Ph3P
AgBF4
1-alkene N
C OR
R = alkyl
Suggs, J. W. J. Am. Chem. Soc. 1978, 100, 640-641
CHOPh2P
+R
R = Alkyl
[(C8H14)2RhCl]2
CPh2PO R
CPh2P ORh
HL2 Cl
Lee, H.; Jun, C.-H. Bull. Korean Chem. Soc 1995, 16, 66
N
CH3
N
H Ph
+R
R = Alkyl
RhCl(PPh3)3N
CH3
N
PhR
Suggs, J. W. J. Am. Chem. Soc. 1979, 101, 489
RhClL3
N
CH3
N
PhRh
H
Cl
L2
N
CH3
N
PhRh
Cl
L2R
RhClL2
-L
R
N
CH3
N
H Ph
N
CH3
N
PhR
CHO
X
X = Br, I
+ R2 R22Pd(OAc)2, Na2CO3
Bu4NCl, DMF, 100oC
O
R1
R2
Larock, R. C.; Doty, M. J.; Cacchi, S. J. Org. Chem. 1993, 58, 4579-4583
Pd(OAc)2
Pd(0)
CHO
Pd X
CHO
Pd-X
R2 R1
Pd-X
R2R1
OH
O
R1
R2
CHO
X
R2 R2Base-HX
Pd
R2R1
O
Annulation Reaction
(CH2)6CO2MeMeO
(CH2)7MeHOCH2
Hg(OAc)2
120oC, 10h
O
(CH2)6CO2Me
(CH2)7Me
OHC (CH2)6CO2Me
(CH2)7Me
(PPh3)3RhCl
(CH2)7Me
O(CH2)6CO2Me
(CH2)6CO2Me
(CH2)7Me
O
RhH (CH2)6CO2Me
(CH2)7Me
RhHCO
(CH2)6CO2Me
(CH2)7Me
30% 30%
Sakai, K.; Ide, J.; Oda, O.; Nakamura, N. Tetrahedron Lett. 1972, 13, 1287-1290
Synthesis of Cyclopentanone Derivatives
CHO + Rh(PMe3)3Cl RhPMe3Cl
Me3P H
PMe3
O
Milstein, D. J. Chem. Soc., Chem. Comm. 1982, 1357-1358
D
O
(PPh3)3RhCl
O
CH3
DCH3H
H
O
RhD Rh
O
CH3D
HH
Campbell, Jr. R. E.; Lochow, C. F.; Vora, K. P.; Miller, R. G. J. Am. Chem. Soc. 1980, 102, 5824-5830
Isolation of intermediate, cis-hydrido pent-4-enoyl rhodium(III) complexes
Stereochemistry of intramolecular hydroacylation
P P
a
e
e
a
S-binap
P P
a
e
e
aRh
t-Bu
H P P
a
e
e
aRh
H
t-BuOO
Barnhart, R. W.; Wang, X.; Noheda, P.; Bergens, S. H.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1994, 116, 1821-1830
C. Decarbonylation through C-H Bond Activation
+RCH2CH2CHO
RCH2CH3 + M-CO
RCH2=CH2 + H2 + M-CO
A
B
MRCH2CH2 C
O
MRCH2CH2 M CO
RCH2CH2 M CO
HH
H
+ArCHO MAr C
O
M
H
Ar M CO
HAr-H + M-CO
Decarbonylation of Aromatic aldehyde
Decarbonylation of Aliphatic aldehyde
Common method for decarbonylation of aldehyde: oxidation of aldehydeand pyrolysis of decarboxylation of the resulting carboxylic acid. Some carboxylic acid is too stable to be decarboyxylated.
Pd/C (5%)
190oC, 2h
57%
27%+
PhCHO
Pd/C (5%)
185oC, 2hPh
37%
CH3(CH2)8 CHO
CH3-(CH2)7-CH3
HC CH2CH3(CH2)7
Tsuji, J.; Ohno, K. A. J. Am. Chem. Soc. 1968, 90, 94
+ (PPh3)3RhClr.t., 24h
+ RhCl(CO)(PPh 3)2 + PPh3
CHO H
Rh(CO)Cl(PPh 3)2 (cat.)+
CHO H
Cl Cl
220oC, 9hCO
Ohno, K.; Tsuji, J. J. Am. Chem. Soc. 1968, 90, 99
only product
stoichiometric reaction
catalytic reaction
RhCl(CO)(PPh 3)2
O2
h[RhClO2(O=PPh3)0.67]x
CO2 + 1.33 Ph3P=O
PPh3
N2
RhCl(PPh3)3
Geoffroy, G. L.; Denton, D. A.; Keeney, M. E.; Bucks, R. R. Inorg. Chem. 1976, 15, 2382
Regeneration of Wilkinson’c complex
OHC
O
MeOH
Me
H
(PPh3)3RhClO
MeOH
Me
H
+CH2Cl2, relux
80%
+ Rh(CO)Cl(PPh3)2
HO
H
CHO
(PPh3)3RhCl+
HO
H
+ Rh(CO)Cl(PPh3)2
CHO
CHO
(PPh3)3RhCl+ + Rh(CO)Cl(PPh3)2PhH, reflux
88%
Use in natural product synthesis
Occidentanol
Lanosterol derivatives
annulene
CDO
Me
Ph
Ph xylene, reflux, 16h
D
Me
Ph
Ph(PPh3)3RhCl
Me
MeO2C CH2CHO
Me
MeO2C CH3
+
94%
+ Rh(CO)Cl(PPh3)2
+ Rh(CO)Cl(PPh3)2(PPh3)3RhCl+CH3CN, relux
64%
Walborsky, H. M.; Allen, L. E. J. Am. Chem. Soc. 1971, 93, 5465. Trost, B. M.; Preckel, M. J. Am. Chem. Soc. 1973, 95, 7862.
Andrews, M. A.; Klaeren, S. A.; J. Chem. Soc., Chem. Comm. 1988, 1266. Andrews, M. A.; Gould, G. L.; Klaeren, S. A. J. Org. Chem. 1989, 54, 5257
Retension of stereochemistry of carbon next to aldehyde
130oC, 5h
Glucose
O
CH2OH
HH
OH
OH
HH
OH
OH
H
(PPh3)3RhCl
+CHO
H OH
HO H
H OH
H OH
CH2OH
NMP
H
H OH
HO H
H OH
H OH
CH2OHArabinitol
88%
(PPh3)3RhCl
Rh(13CO)Cl(PPh3)2
Rh(CO)Cl(PPh3)2
NMP =N
Me
O
13CH2OH
O
HO H
H OH
H OH
CH2OH
130oC, 2h
NMP
(PPh3)3RhCl
+13CHO
O
HO H
H OH
H OH
CH2OH
2(PPh3)3RhCl
CH3
H OH
H OH
CH2OH
+
+ Rh(CO)Cl(PPh3)2
-2H2O
O CH2OHOHC (PPh3)3RhCl O CH2OH
ºÎ ¹ÝÀÀ
ÁÖ¹ÝÀÀ
79%
furfuryl alcohol
1-deoxyerythritol
5%
-H2
Fructose
0.002% without NMP
Ph CHO
or
CH3(CH2)5-CHO
[Rh(dppe)2]+l
or [Rh(dppp)2]+
115-180oC
Ph H
or
CH3(CH2)4CH3
dppe = Ph2PCH2CH2PPh2 dppp = Ph2PCH2CH2CH2PPh2
Doughty, D. H.; Pignolet, L. H. J. Am. Chem. Soc. 1978, 100, 7083
Since the bond of common Rh and CO bond is very strong, it is hard toLiberate CO. But CO binded to Rh+ species are easily to be dissociatedDue to weak -back donation.
[Rh(dppp)2]+Cl-
NH
CH3OBr
CO2Eta) LiAlH4
b) MnO2 NH
CH3OBr
CHO
xylene, relux, 18hNH
CH3OBr
77% 95%
(4 mol%)
Meyer, M. D.; Kruse, L. I. J. Org. Chem. 1984, 49, 3195
CH2CHO
H3C CH3
CH3
CH3
H3C CH3
CH3
99%
(PPh3)3RhCl+
DPPA
O
PN3PhO
PhO
THF, r.t. , 45h
O
PNCOPhO
PhO+
O'connor, J. M.; Ma, J. J. Org. Chem. 1992, 57, 5075
Elimination of carboxylic ester
Elimination of aldehyde under very mild conditions
isocyanate
RhPPh3Cl
Ph3P CORh
PPh3Cl
Ph3P L
R H
OR-H
O
PN3PhO
PhO
O
PNCOPhO
PhO
RhPPh3Cl
Ph3P CO
O
PN3PhO
PhO
RhPPh3Cl
Ph3P N
CO
N N
PO
OPh
OPhRh
PPh3Cl
Ph3P N2
O
PNCOPhO
PhO
+
H C
O
O-CH2CH2PhRu3(CO)12, (CH3)3NO.2H2O
200oc, 6h, ArHO-CH2CH2Ph
100%
[Ru] C
O
O-CH2CH2PhH [Ru] O-CH2CH2PhH
CO
Kondo, T.; Tantayanon, S.; Tsuji, Y.; Watanabe, Y. Tetrahedron Lett. 1989, 30, 4137
(CH3)3NO is a promoter to make unsaturation of Ru3(CO)12.
CHO [Rh(CO)(triphos)][SbF6] (5 mol%)
diglyme, reflux, 48h
triphos =Ph2P
PPPh2
Ph
100%
Beck, C. M.; Rathmill, S. E.; Park, Y. J.; Chen, J.; Crabtree, R. H. Organometalics 1999, 18, 5311
Retard the formation of byproducts