synlett 07/2007 - Thieme Chemistry

SYNLETT
Accounts and 2007
Rapid Communications in No. 7
Synthetic Organic Chemistry April II
999 K. Kaneda* Cation-Exchanged Montmorillonites as Solid Acid Catalysts for Organic
Synthesis
1016 P. Langer* Domino Reactions of 1,3-Bis(silyl enol ethers) with 4-(Trialkylsilyloxy)benzopyrylium
Triflates
1026 Z. Huang*
J. E. Reilly
R. N. Buckle
OH
Me3SiO
Me3SiO
O
OSiMe3 OMe
OSiMe3
OEt
O
O
N
O
OH
OMe
O
OEt
OSiMe3 R
OTf –
+
O
R = H, CN, CHO
Me3SiO
Me3SiO
OH
O O
OSiMe3
OMe
OSiMe3
OMe
Cl
O
O O
An Efficient Synthesis of Amides and Esters via Triacyloxyboranes
RCO2H
1. BH3, toluene, r.t.
2. R 1 R 2 NH or R 3 OH
RCONR 1 R 2 or RCO 2R 3
Accounts
Letters

Letters
VI Table of Contents
1031 A. Arcadi*
G. Bianchi
A. Inesi
F. Marinelli
L. Rossi*
1037 H. Habib-Zahmani
J. Viala*
S. Hacini
J. Rodriguez*
1043 R. Hodgson
A. Kennedy
A. Nelson*
A. Perry*
1047 S. Perrone
A. Metzger
P. Knochel*
Sequential Alkylation/Heterocyclization of b-(2-Aminophenyl)-a,b-ynones
Promoted by Electrogenerated Carbanions: A New Approach to
Functionalized 4-Alkylquinolines
R-H
electrolysis
R 2
R 3
Synthesis of Functionalized Spiroheterocycles by Sequential
Multicomponent Reaction/Metal-Catalyzed Carbocylizations from
Simple b-Ketoesters and Amides
X
O O
Br
( )n
z
+
Y R
+
ArCHO
DBU
THF–MeOH
Ar
X
O
( ) n
O
z
Y
NH 2
O
R 1
R 2
RCM
Ar
YR = N(allyl)Me
= O(allyl)
Heck
R YR = N(allyl)Me
Buchwald
YR = NHPh
Ar
R 3
X
O
Ar
X
O
( )n
R
N
O
X
O
O
Y
R 1
N
O
N Ph
Synthesis of 3-Sulfonyloxypyridines: Oxidative Ring Expansion of a-Furylsulfonamides
and N→O Sulfonyl Transfer
O
R
NHTs
NBS
or
MCPBA
O
HO N R
Ts
R = alkyl, aryl or heteroaryl
Chiral Allylic Cyanohydrins as Versatile Substrates for Diastereoselective
Copper(I)-mediated S N2¢ Allylic Substitutions
2,6-F 2C 6H 3
O
O
CN
R2Zn (2.4 equiv)
CuCN·2LiCl (1.2 equiv)
n Me
THF–NMP (2:1)
–30 °C
n
n = 1, 96% ee
n = 0, 90% ee
AlCl3
CN
R
Me
up to 96% ee
40–91% yield
N
OTs
R

Table of Contents VII
1051 F. Oswald
P. de la Cruz
F. Langa*
1055 S.-A. Kim
H. M. Lee
J.-S. Ryu
H. S. Kim*
1059 E.-A. Jo
E.-G. Cho
C.-H. Jun*
1063 N. Kolocouris*
G. Zoidis
C. Fytas
Nitration of Fullerene Derivatives under Mild Conditions
R
N
N
NO 2
Me4N + NO3 –
Tf 2O, CH 2Cl 2
Synthesis of Conformationally Locked Methanocarba-uridine as a Precursor
for Nucleotides Agonizing P2Y 6 Receptor
BnO
HO
OH
BnO
TsO
N3
R
N
O2N
NH
HO N
O
OBz
O
a precursor for
methanocarba-uridine nucleotides
Orthoalkylation of Aromatic Ketimine with the Vinyl Group in
Polybutadiene Using a Rhodium(I) Catalyst
Ph
Ph
a b
Ph
R 2
O
+
1) (Ph 3P) 3RhCl
130 °C, 3 h
2) H + /H 2O
a b c Ph
d
R 1
Facile Synthetic Routes to 2-Oxo-1-adamantanalkanoic Acids
O
[Me3Si]2NLi
MeCOOMe
THF, –75 °C
30 min
(98%)
i) BrMg-C
ii) NH4Cl, H2O (82%)
CCH2OMgBr,
THF
MeOOCH 2C
endo/exo
OH
exo
C C–CH2OH
OH
Ph
R 2
N
R 1
N
O
CH 2COOH
O
NO 2
(overall yield 76%)
CH2CH2COOH
O
(overall yield 67%)
Letters

Letters
VIII Table of Contents
1067 M. Kueny-Stotz
G. Isorez
S. Chassaing*
R. Brouillard
1071 T. K. Pradhan
A. Hassner*
1075 M. Kikuchi
T. Inagaki
H. Nishiyama*
1079 V. Sridharan
C. Avendaño
J. C. Menéndez*
Straightforward Synthesis of Highly Hydroxylated Phloroglucinol-Type
3-Deoxyanthocyanidins
HO
OH
OH
R = H, OTBS
O
R
HPF6
AcOH
r.t., 24 h
HO
OH
+
O
R' = H, OH
PF 6 –
82–91% (4 examples)
Stereoselective Synthesis of Medium-Sized Carbocycles Using Alkoxy
Radical Fragmentation as a Key Methodology
HO
( )n
EtO2C n = 1,2
OAc
DIB, I 2, CH 2Cl 2
hν
40–93%
OHC
( ) n
I
OAc
CO 2Et
Et 3N, CH2Cl2
90–95%
OHC
( ) n
I
CO 2Et
Asymmetric Intramolecular Michael Reaction Catalyzed by Proline-Derived
Small Anilides
H
O
O
R'
N
H
O
R
N
H
1 R
(30 mol%)
AcOH (30 mol%)
CHCl 3–H2O, 30 °C
R = H, Me, Et, i Pr
H
O
*
O
*
R'
> 90% yield
up to 90% de
up to 93% ee for trans
CAN-Catalyzed Vinylogous Povarov Reactions: The First Three-Component
Synthesis of 2-Functionalized Tetrahydroquinolines from Anilines,
Cinnamaldehyde and Vinyl Ethers
R 1
NH2
OR 2
O
H
CAN (5–15%)
MeCN, r.t.
R 1
H
N
H
OR 2
H
R'

Table of Contents IX
1083 D. Padmakshan
S. A. Bennett
G. Otting*
C. J. Easton*
1085 S. Hübner
H. Neumann
D. Michalik
S. Klaus
D. Strübing
A. Spannenberg
A. Jacobi von Wangelin
M. Beller*
1091 N. Schwarz
K. Alex
I. A. Sayyed
V. Khedkar
A. Tillack
M. Beller*
1096 M. Shindo*
K. Yaji
T. Kita
K. Shishido
Stereocontrolled Synthesis of (S)-g-Fluoroleucine
a) protection
b) NBS
c) AgF
d) deprotection
F
+
H3N CO –
2
+
H3N CO –
2
Three-Component Reactions of a- and b-Bromo Aldehydes with Amides and
Dienophiles – An Easy Way to Versatile 1-Amido-2-Cyclohexenes
R 1
O
NHR 2
+
H
O
Br
1.0 equiv 2.0 equiv 1.5 equiv
R 3
R 4
+
O
O
N
toluene
150 °C, 20 min
0.5 mmol/mL
MW
Titanium-Catalyzed Hydroamination of Propargyl Alcohol Derivatives:
Synthesis of 3-Silyloxy-2-methylindoles via Hydrohydrazination
TBDMSO
N R2 R
H2N
1
+
1. Ti(NEt2)4, 2,6-di-tert-butyl-
4-methylphenol, toluene
2. ZnCl2, toluene, 100 °C, 24 h
R 1
Br
R 3
N
R1 O
NR 2
R 4
OTBDMS
Acid-Catalyzed Nazarov Reaction Controlled by b-Alkoxy Groups
O
OR
acid catalyst
(0.001 mol% to 10 mol%)
< 3 min
r.t.
RO
O
64–96% yield
R 2
Me
O
O
N
Letters

Letters
X Table of Contents
1101 C. Camarero
I. González-Temprano
E. Lete*
N. Sotomayor
1106 T. A. Stroganova
A. V. Butin*
V. K. Vasilin
T. A. Nevolina
G. D. Krapivin
1109 S. Shafi
A. H. Banday
T. Ismail
H. M. S. Kumar*
1112 K. R. Prasad*
M. G. Dhaware
Stereoselective Conjugate Additions to g-Lactams: Synthesis of
Polysubstituted Benzo-Fused Indolizidine Systems
MeO
MeO
R 1
–
Z Z'
N
MeO
MeO
R1 O
MeO
R
N
O
CO2R = Me, Bu
Z, Z' = CN, CO2Me, COMe, CO2Et, H
1
MeO
R
N
O
1
and/or
Z
Z'
CO2R
Z
Z'
CO2R A New Strategy for Pyrrolo[1,2-a][1,4]diazepine Structure Formation
NH 2
O
H
N
O
HCl
AcOH
Domino Addition/N–C Heterocyclization of Azides with Allenyl Magnesium
Bromide: Rapid Synthesis of 5-Butynyl-1,2,3-triazoles
R
– +
N N N
+
MgBr
N
O
NH
THF, r.t.
R
N
N
Stereoselective Total Synthesis of (–)-9-Deoxygoniopypyrone
O
O
NMe 2
O
O
NMe2
HO
HO
Ph
OMe
OH
O
H
O
Ph
O
O
HO H
9-deoxygoniopypyrone
N

Table of Contents XI
1115 S. Li
J. Li
X. Jia*
1118 A. R. Hajipour*
F. Rafiee
A. E. Ruoho
1121 G. Coste
S. Gerber-Lemaire*
1124 P. Brémond
G. Audran*
Y. Aubin
H. Monti
Samarium Metal Promoted Facile C-Acetylation of Baylis–Hillman Adducts
in the Presence of Iron(III) Chloride and Iodine
R
OH
COOMe
Sm(0), Ac 2O, FeCl 3, I 2
THF, reflux
R
COOMe
O + R
COOMe
Facile and Selective Oxidation of Benzylic Alcohols to Their Corresponding
Carbonyl Compounds with Sodium Nitrate in the Presence of Brønsted
Acidic Ionic Liquids
X
CH2OH
Me
N
+ NaNO3 +
N
H
HSO 4 –
40 °C
grinding
Efficient Synthesis of Cyclic Glycolipid Analogues
PO
P = BOM
OH
O
OH OH O
OH
OP
7 steps
9–11%
PO
X
50–97%
O
O
CHO
OH OH O
O
N
N
H ( )n H
Total Chemoenzymatic Synthesis of (–)-3¢-Methylaristeromycin
EtO 2C
S R
OH
8 steps
43%
AcO
O O
OTf
3 steps
53%
HO
3'
HO OH
N
N
NH 2
N
(–)-3'-methylaristeromycin
N
OP
Letters

Letters
Clusters
XII Table of Contents
1127 J. González Marrero
L. San Andrés*
J. Gutiérrez Luis
1130 T. Harada*
C. Kitano
K. Mizunashi
1135 Y. K. Kang
M. J. Cho
S. M. Kim
D. Y. Kim*
1139 K.-i. Moriya
Y. Hamashima
M. Sodeoka*
Oxidative C-Ring Opening of Abietane Diterpenes with Ammonium
Cerium(IV) Nitrate
MeO
O
H
MeO
O
H
O
O
OMe
OMe
O
CAN
MeCN–H2O (2:1)
CAN
MeCN–H 2O (2:1)
O
O
H
H
COOMe
O
COOMe
O
O
OH
COOMe
Iodine-Atom-Transfer-Type Carbocyclization of 2-(2-Propynyloxy)ethyl
Iodides Involving a Lithium Alkylidene Carbenoid Intermediate
R1 R2 O
R 3
H
I
Bu I
Bu Li
THF, 40 °C
(1.1 equiv)
(0.4 equiv)
Asymmetric Electrophilic Fluorination of a-Cyanoalkylphosphonates
Catalyzed by Chiral Palladium Complexes
O
(EtO) 2P CN
Ar
(PhSO2) 2NF
(R)-xylyl-BINAP-Pd (II)
EtOH, r.t.
O
(EtO)2P
*
CN
2,6-di-tert-butyl-4-methylpyridine
Ar F
Pd(II)-Catalyzed Asymmetric Fluorination of a-Aryl-a-cyanophosphonates
with the Aid of 2,6-Lutidine
(EtO) 2P
F
O
CN
Ar
+
SO2Ph N
SO2Ph *
P
P
Pd(II)
2,6-lutidine (1 equiv)
EtOH, –20 °C
5 mol% in Pd
R 3
O
(EtO)2P
O
R 2
∗
Ar F
~ 98% yield
~78% ee
R 1
CN
O
I
I

Table of Contents XIII
1143 J. Ramírez
D. P. Huber
A. Togni*
1148 A. Hidaka
B. Zagipa
H. Nagura
T. Fuchigami*
1153 N. Shibata*
H. Yasui
S. Nakamura
T. Toru*
1158 G. K. S. Prakash*
P. J. Linares-Palomino
K. Glinton
S. Chacko
G. Rasul
T. Mathew
G. A. Olah*
Asymmetric Electrophilic Fluorination of a-Nitro Esters
O 2N
R
1. base
O
O
2. Selectfluor
O2N O
O
® ,
cinchona alkaloid
R F
R = Me, i R
Pr, Ph, Bn
2
R1 R
O N
3
1 2
cinchona alkaloid
CD: R1 = H, R2 = H, R3 = vinyl
QN: R1 = H, R2 = OMe, R3 = vinyl
HQCB: R1 = p-ClBz, R2 = OMe, R3 MeCN–H2O or
THF, MeCN
up to 91% yield
up to 40% ee
AcCD: R
= Et
1 = Ac, R2 = H, R3 = vinyl
AcQN: R1 = Ac, R2 = OMe, R3 = vinyl
Regioselective Anodic Fluorination of a-(Arylthio)benzylphosphonate
Esters, a-(Arylthio)methylphosphonate Esters and Their Analogues
Y
ArS P(O)(OEt)2
Y = H, Ar
– 2e – , – H + , F –
Y F
DME or MeNO 2 ArS P(O)(OEt) 2
DNA-Mediated Enantioselective Carbon–Fluorine Bond Formation
Friedel–Crafts Alkylations of Arenes with Mono- and Bis(trifluoromethyl)oxiranes
in Superacid Medium: Facile Synthesis of a-(Trifluoromethyl)-
and a,a-Bis(Trifluoromethyl)-b-Arylethanols
R 2
R 1
+
R 1 = H, Me, Et, n-Pr
R 2 = H, Me
O X CF3SO3H
Y
CH 2Cl 2,
0 °C to r.t.
R 1
R 2
70–95% yield
OH
X
Y
X = CF3, Y = H, CF3
Clusters

Clusters
Spotlights
XIV Table of Contents
1163 M. Shimizu*
M. Higashi
Y. Takeda
G. Jiang
M. Murai
T. Hiyama
1166 S. Purser
C. Wilson
P. R. Moore
V. Gouverneur*
1169 T. Mori
J. Ichikawa*
1172 Compiled by
D. Rodrigues da Rocha
Novel Generation of 3,3,3-Trifluoropropynyllithium and Transformation of
the Carbonyl Adducts to Trifluoromethyl-Substituted Allenes
Cl
Cl
O
CF3
1) TsCl
Et3N
2) 2 BuLi
Li
CF3
1) R 1 R 2 CO
2) TsCl or MsCl
Et3N
3) R 3 ZnCl
Pd cat.
Highly Diastereoselective Electrophilic Fluorination of Cyclic
syn-b-Hydroxysilanes
SiMe 2R 1
() n
OR 2
Selectfluor ® (1.1 equiv),
NaHCO3 (1.2 equiv)
MeCN, r.t., 72 h
n = 1 or 2
OR 2
()
F n
yields up to 90%
dr up to > 98:2
ee up to 86%
Radical 6-endo-trig Cyclization of b,b-Difluoro-o-isocyanostyrenes:
A Facile Synthesis of 3-Fluoroquinolines and Their Application to the
Synthesis of 11-Alkylated Cryptolepines
F2C
C
R
N
F
F
n-Bu 3Sn
n-Bu3SnH cat. AIBN
R
N
n-Bu3Sn
i) EX
ii) DBU
R
δ+ δ–
F2C
Oxalyl Chloride: A Versatile Reagent in Organic Synthesis
F
E
N
R
N
R 1
R 2
CF 3
R 3

Table of Contents XV
1174 Compiled by
P. Devi
1176 Erratum
Nitromethane (MeNO 2)
XVII Forthcoming Articles
Spotlights

XVI Table of Contents
Author Index
Alex, K. 1091
Arcadi, A. 1031
Aubin, Y. 1124
Audran, G. 1124
Avendaño, C. 1079
Banday, A. H. 1109
Beller, M. 1085, 1091
Bennett, S. A. 1083
Bianchi, G. 1031
Brémond, P. 1124
Brouillard, R. 1067
Buckle, R. N. 1026
Butin, A. V. 1106
Camarero, C. 1101
Chacko, S. 1158
Chassaing, S. 1067
Cho, E.-G. 1059
Cho, M. J. 1135
Coste, G. 1121
de la Cruz, P. 1051
Devi, P. 1174
Dhaware, M. G. 1112
Easton, C. J. 1083
Fuchigami, T. 1148
Fytas, C. 1063
Gerber-Lemaire, S. 1121
Glinton, K. 1158
González Marrero, J. 1127
González-Temprano, I. 1101
Gouverneur, V. 1166
Gutiérrez Luis, J. 1127
Habib-Zahmani, H. 1037
Hacini, S. 1037
Hajipour, A. R. 1118
Hamashima, Y. 1139
Harada, T. 1130
Hassner, A. 1071
Hidaka, A. 1148
Higashi, M. 1163
Hiyama, T. 1163
Hodgson, R. 1043
Huang, Z. 1026
Huber, D. P. 1143
Hübner, S. 1085
Ichikawa, J. 1169
Inagaki, T. 1075
Inesi, A. 1031
Ismail, T. 1109
Isorez, G. 1067
Jacobi von Wangelin, A. 1085
Jia, X. 1115
Jiang, G. 1163
Jo, E.-A. 1059
Jun, C.-H. 1059
Kaneda, K. 999
Kang, Y. K. 1135
Kennedy, A. 1043
Khedkar, V. 1091
Kikuchi, M. 1075
Kim, D. Y. 1135
Kim, H. S. 1055
Kim, S. M. 1135
Kim, S.-A. 1055
Kita, T. 1096
Kitano, C. 1130
Klaus, S. 1085
Knochel, P. 1047
Kolocouris, N. 1063
Krapivin, G. D. 1106
Kueny-Stotz, M. 1067
Kumar, H. M. S. 1109
Langa, F. 1051
Langer, P. 1016
Lee, H. M. 1055
Lete, E. 1101
Li, J. 1115
Li, S. 1115
Linares-Palomino, P. J. 1158
Marinelli, F. 1031
Mathew, T. 1158
Menéndez, J. C. 1079
Metzger, A. 1047
Michalik, D. 1085
Mizunashi, K. 1130
Monti, H. 1124
Moore, P. R. 1166
Mori, T. 1169
Moriya, K.-i. 1139
Murai, M. 1163
Nagura, H. 1148
Nakamura, S. 1153
Nelson, A. 1043
Neumann, H. 1085
Nevolina, T. A. 1106
Nishiyama, H. 1075
Olah, G. A. 1158
Oswald, F. 1051
Otting, G. 1083
Padmakshan, D. 1083
Perrone, S. 1047
Perry, A. 1043
Pradhan, T. K. 1071
Prakash, G. K. S. 1158
Prasad, K. R. 1112
Purser, S. 1166
Rafiee, F. 1118
Ramírez, J. 1143
Rasul, G. 1158
Reilly, J. E. 1026
Rodrigues da Rocha, D. 1172
Rodriguez, J. 1037
Rossi, L. 1031
Ruoho, A. E. 1118
Ryu, J.-S. 1055
San Andrés, L. 1127
Sayyed, I. A. 1091
Schwarz, N. 1091
Shafi, S. 1109
Shibata, N. 1153
Shimizu, M. 1163
Shindo, M. 1096
Shishido, K. 1096
Sodeoka, M. 1139
Sotomayor, N. 1101
Spannenberg, A. 1085
Sridharan, V. 1079
Stroganova, T. A. 1106
Strübing, D. 1085
Takeda, Y. 1163
Tillack, A. 1091
Togni, A. 1143
Toru, T. 1153
Vasilin, V. K. 1106
Viala, J. 1037
Wilson, C. 1166
Yaji, K. 1096
Yasui, H. 1153
Zagipa, B. 1148
Zoidis, G. 1063