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R6
O O R5 R2
cat. [ReBr(CO)3(thf)]2
R1 OEt + R3 R4 + R5 R6
R2 R1 R4
R3
Current Literature
Kalyani Patil
6/28/08
• Title Paper
• Summary
Trimerization of acetylenes
R1
R1
+
CpCo(CO)2
CH2
Vollhardt Angew. Chem. Int. Ed.
(CH2)n
30 - 95% R2 1984, 23, 539
R2
+ + MLx-2
MLx MLx-1 MLx-2
1 2 3
+ +
• Oxidative coupling to give metallacyclopentadiene
MLx-2 MLx-2
• Alkyne insertion or Diels-Alder type addition
5 4
MLx-2
+ t-BuCl ReBr(CO)5 (1 mol%) Sonoda et. al. Bull. Chem. Soc. Jpn.
ClCH2CH2Cl, 84 °C
93%
t-Bu 2000, 73, 2779
OCH3 OCH3
1 mol% (dppm)ReOCl3
OH O Cl
Toste et. al. J. Am. Chem. Soc.
Ph Cl OH Ph
H H 2003, 125, 6076
n-Bu MeCN, 65 °C n-Bu
78%
[M]
OH [M] O O O O
X O [3,3] R1 H+
[M]
R1 R1 O R1 R2
-HX
R2 R2 1 R2 2
[O] R3OH
O OR3
R1 R1
3 R2 R2
Synthesis of 1,5-Enynes
5 mol% (dppm)ReOCl3
OH
Ph TMS cat. NH4PF6
Ph
Toste et. al. J. Am. Chem. Soc.
+
H
MeNO2, 65 °C
H 2003, 125, 15760
Ph 79% Ph
OEt
87% 78% 78% 61%
O O O OH O
R
OEt OEt
O
(4-b)
HO OEt
R Re (I)
R
O (4-a)
OEt
(3-b)
• Rhenacyclopentene intermediate
HO Re
R HO
O (2-b)
R • Retro-aldol reaction/isomerization
O
OEt OEt
(2-a)
• Reductive elimination
O HO
Re Re
R (3-a) R
O O
OEt OEt
t-Bu HN t-Bu
N
+ Ph Me
cat. [ReBr(CO)3(thf)]2
Ph
Takai et. al. J. Am. Chem. Soc.
H
toluene, reflux, 24h
95%
2005, 127, 13498
O cat. [ReBr(CO)3(thf)]2
+ CO2Et
p-anisidine (15 mol%)
CO2Et Takai et. al. Angew. Chem. Int. Ed.
toluene, 180 °C, 24h
93% 2006, 45, 2766
Synthesis of isobenzofuran
Ph O cat. [ReBr(CO)3(thf)]2 Ph
N
Ph
+ Ph
MS 4Å Takai et. al.J. Am. Chem. Soc.
H toluene, reflux, 24h
93%
O
2006, 128, 12376
Ph
1. Me Me Ph Ph CO2Et CO2Et 83
2. Ph Me Ph Ph CO2Et CO2Et 64
3. Me H Ph Ph CO2Et CO2Et 84
4. Me Me Me Ph CO2Et CO2Et 91
5. Me Me H Ph CO2Et CO2Et 87
9. Me Me Ph Ph CO2Et H 83
Ph n-C5H11 Ph Ph Ph Ph Ph
n-C6H13 n-C6H13 Ph Ph
A B C D
Kuninobu, Y.; Takata, H.; Kawata, A.; Takai, K. Org. Lett. ASAP
SiMe3
, CsF(3 eq.) Ph R time (h) yield (%)
OTf Me (1a) 24 92 (2a)
(1.5 eq.) Ph Ph (1b) 48 96 (2b)
toluene/CH3CN, 20 °C, 12h R
2
Intramolecular Reaction
O
O O
[ReBr(CO)3(thf)]2 (2.5 mol%) O
OEt Ph MS 4Å (100 wt%-Re cat)
toluene, 150 °C, 24h
Ph
Synthesis of tetrahydronaphthalene
derivatives
CO2Me
MeO2C CO2Me MeO2C
(4 eq.) (84%)
toluene, 150 °C, 48h
Ph
Kuninobu, Y.; Takata, H.; Kawata, A.; Takai, K. Org. Lett. ASAP
O O OH O
R1 OEt R1 OEt
O R6 R2 R2
O R2 (6) R5 R2
R5
R6 R4
R3 -CO2 (1)
R3 • Rhenacyclopentene intermediate
R1 R4 Re (I)
R1 R4
R3
(5) R5 R6 • Retro-aldol reaction/reductive
O elimination
R2 R1 R2 R1 R2
O O CO2Et O CO2Et
H (2-b) H
Re R4
• Isomerization of the alkene/cyclization
R1 R4
R3 R4
R3 R3
(3-b) • DA reaction/decarboxylation
(4) (2-a)
-EtOH
O
EtO R2 R2 CO2Et
O H (3-a) R1 Re
R4
R1 R4
O R3
R3
Kuninobu, Y.; Takata, H.; Kawata, A.; Takai, K. Org. Lett. ASAP
Kalyani Patil @ Wipf Group Page 12 of 13 7/3/2008
Summary