Tetrahedron Letters Vol. 48, No.

47, 2007

Contents

COMMUNICATIONS
Ruthenium-catalysed synthesis of tertiary amines from alcohols pp 8263–8265
M. Haniti S. A. Hamid and Jonathan M. J. Williams*

R2 Ru cat. R2
R1 OH + HN R1 N
R2 R2

Secondary amines have been alkylated with alcohols using borrowing hydrogen methodology.

Rhodium-catalyzed addition of aryl boronic acids to 1,2-diketones and 1,2-ketoesters pp 8266–8269

Gregory R. Ganci and John D. Chisholm*

3 mol %
O OH
B(OH)2 Rh(acac)(CO)2
6 mol % PPh(Cy)2
+
DME/H2O O
O 80 °C

Asymmetric synthesis of (+)-iso-6-cassine via stereoselective intramolecular amidomercuration pp 8270–8273

Satwinder Singh, Om V. Singh and Hyunsoo Han*

TCA O
resolution Hg(TFAO)2 H
O O NH N
Overman metathesis 9
OH OPMB OH

8253
8254 Contents / Tetrahedron Letters 48 (2007) 8253–8261

Rendering a calixarene having dipyridyl pendants soluble in water results in different species with smaller pp 8274–8276
binding constants
Giuseppe Arena, Annalinda Contino,* Giuseppe Maccarrone, Domenico Sciotto
and Carmelo Sgarlata N N

A novel dipyridyl-based sulfonato-calixarene is able to complex Co(II) and Cu(II) in water. N N

-O S
3
SO3-

O O

O O

O - O
-O S SO3
3

One-pot synthesis of b-amino acid derivatives via addition of bis(O-silyl) ketene acetals on iminium salts pp 8277–8280
Roba Moumné, Bernard Denise, Andrée Parlier, Solange Lavielle, Henri Rudler and
Philippe Karoyan*

Diamond projection of a,b-unsaturated d-amino acid derivative.

Highly efficient microwave-accelerated preparation of b-ketoimines pp 8281–8284

Dong Hwan Lee, Sang-Eon Park, Kyuho Cho, Younsoo Kim, Taimur Athar and Ik-Mo Lee*

R1 R2 R1 R2
microwave
+ HN R3
2
O O solvent free O HN
R3

Carbamoyl radicals from carbamoylxanthates: a facile entry into isoindolin-1-ones pp 8285–8289

Germán López-Valdez, Simón Olguı́n-Uribe and Luis D. Miranda*

Me O S OEt O O
Lauroyl
peroxide Me Me
TFMSA
N S N t-Bu NH
t-Bu 77% 97%
 Contents / Tetrahedron Letters 48 (2007) 8253–8261 8255

Pauferrol A, a novel chalcone trimer with a cyclobutane ring from Caesalpinia ferrea mart exhibiting pp 8290–8292
DNA topoisomerase II inhibition and apoptosis-inducing activity
Hiroshi Nozaki,* Ken-ichiro Hayashi, Masahiro Kido, Kazuyuki Kakumoto, Shogo Ikeda,
Nobuyasu Matsuura, Hiroyuki Tani, Daisuke Takaoka, Munekazu Iinuma and Yukihiro Akao
OH

Pauferrol A
HO
Pauferrol A showed potent human topoisomerase II inhibitory activity and OH
induction of apoptosis in human leukemia HL60 cells. O
OH HO
O O
HO O

HO OH

Stereoselective nitration of asymmetric hydrazones with nitric oxide pp 8293–8296

Wen-tao Wu, Gang Su, Zhou Lu and Long-min Wu*

Ar Ar Ar
HN N N
N N NO2 N NO2
NO, cat. O2 R +
R R
CH2Cl2, r.t.
n n n
1 trans-2 cis-2
n = 1, 2, 3
Ar = 2,4-dinitrophenyl

Nitration of asymmetric hydrazones with nitric oxide occurred stereoselectively, giving mono-nitrated trans isomer as a major
outcome. The ratio of trans to cis was up to >99.

Total synthesis of the novel seco-prezizaane sesquiterpenoid (+)-1S-minwanenone pp 8297–8300

Goverdhan Mehta* and Harish M. Shinde

The first total synthesis of (+)-1S-minwanenone, an archetypical seco-prezizaane sesquiterpene, has been accomplished from a
readily available chiral endo-tricyclic synthon following a flexible strategy.

The first examples of cyclizations of a glycal with enamines leading to oxa-aza bicyclononene scaffolds pp 8301–8305
J. S. Yadav,* B. V. Subba Reddy, M. Srinivas, Ch. Divyavani, A. C. Kunwar and Ch. Madavi

O
O Ph
O
AcO Me NH2 InCl3 AcO N
+ + Me
AcO O Me DCE, 80 °C AcO
OAc Me
O
8256 Contents / Tetrahedron Letters 48 (2007) 8253–8261

Niobium(V) pentachloride: an efficient catalyst for C-, N-, O-, and S-nucleophilic substitution reactions pp 8306–8310
of benzylic alcohols
J. S. Yadav,* Dinesh C. Bhunia, K. Vamshi Krishna and P. Srihari

OH Nu O R"
R' Nu-H or R"-OH NbCl5, CH3CN R'
R + or
r.t., 0.1 to 2 h R or R
R'
NH4SCN or NaN3
70-95%
X
R = H, OH, OMe R'
or R
R' = H, Me, Ph
Nu-H = 2-naphthol, indole, resorcinol, anisole, PhSH
R" = allyl, propargyl, 3-benzyloxypropyl X = SCN, N3

Reaction of selenofenchone with propiolic acid: first instance of Wagner–Meerwein rearrangement in pp 8311–8313
selone
Kentaro Okuma,* Yuichi Mori, Toshiyuki Shigetomi, Miki Tabuchi, Kosei Shioji and
Yoshinobu Yokomori

H
C
+ O O +
C O OH
Se COOH Se
Se
in chloroform 48% 13%
no solvent 0% 97%

The first asymmetric esterification of free carboxylic acids with racemic alcohols using benzoic pp 8314–8317
anhydrides and tetramisole derivatives: an application to the kinetic resolution of secondary benzylic
alcohols
Isamu Shiina* and Kenya Nakata

Efficient, solventless N-Boc protection of amines carried out at room temperature using sulfamic acid as pp 8318–8322
recyclable catalyst
Dharita J. Upadhyaya, Alessandro Barge, Rachele Stefania and Giancarlo Cravotto*

Sulfamic acid (5 mol %), Solventless

(R)ArNH2 + (Boc)2O (R)ArNHBoc
RT, 1 - 30 min, ((((
85-100%
 Contents / Tetrahedron Letters 48 (2007) 8253–8261 8257

Reduction of pentafluorophenyl esters to the corresponding primary alcohols using sodium borohydride pp 8323–8325
Eleni Papavassilopoulou, Petros Christofis, Despina Terzoglou and Panagiota Moutevelis-Minakakis*

OH
F F

F F
O O F F
F NaBH4, THF, rt
R R R OH
OH DCC O F 15 min-4.0 h

F F

The reduction of a variety of pentafluorophenyl esters of carboxylic acids, including N-protected amino acids, by NaBH4 in THF
has been developed.

Various P*-chiral phosphite-type ligands: their synthesis, stereochemistry and use in Pd-catalysed pp 8326–8330
allylation
Eduard B. Benetsky,* Sergey V. Zheglov, Tatiana B. Grishina, Fliur Z. Macaev, Liudmila P. Bet,
Vadim A. Davankov and Konstantin N. Gavrilov
Various P*-chiral phosphite-type ligands used in Pd-catalysed allylation

O O O O O
P OMe P OMe P NEt2 P OMe P OMe
O O O O Ph O
1 2 3 4 5

O
Ph O O O O O
P OMe P OMe P OMe P OMe O
N Ph N N N O
Ph P OMe
N
6 7 8 9 10

A convenient route to prepare isodicyclopentadiene—precursor of 1,5-dihydro-pentalene pp 8331–8333

F. Burgos O,* I. Chávez, J. M. Manrı́quez* and S. Alegrı́a

Secondary alcohols act as better nucleophiles than primary alcohols in the lipase-catalyzed regioselective pp 8334–8337
deacylation of dihydroxybenzenes acylated at both phenolic hydroxyls
Toshifumi Miyazawa,* Manabu Hamada, Ryohei Morimoto, Takashi Murashima and Takashi Yamada

OCOC2H5 OH OCOC2H5 OCOC2H5

C(CH3)3 C(CH3)3
(CH3)2CHOH (CH3)2CHOH

CAL-B, 60 min CAL-B, 60 min

OCOC2H5 OCOC2H5
C2H5 C2H5 OCOC2H5 OH

100% 97%
8258 Contents / Tetrahedron Letters 48 (2007) 8253–8261

Synthesis, X-ray crystallographic analysis, and theoretical structure analysis of tetrathienylethenes pp 8338–8342
designed for photo- and electrochromism
Hiroshi Ikeda,* Azusa Sakai, Hayato Namai,
Akinori Kawabe and Kazuhiko Mizuno* R S S R UV (λ = 350 nm) R S S R

Photochromism
Vis (λ = 490 nm)
R S S R R S S R
or heating
3b, R = SMe Electrochromism 4b, R = SMe
open form closed form
SET Oxidation
λab = 327 nm (sh) λab = 489 nm

Eap = ca. +0.76 V SET Oxidation Eap = ca. +0.21 V

Rapid syntheses of (±)-pterocarpans and isoflavones via the gold-catalyzed annulation of aldehydes and pp 8343–8346
alkynes
O O
Rachid Skouta and Chao-Jun Li* cat. AuCN
R
1. [H]
O 2

H R2
R1 R1
+
2. H+ R1
OH O O
isoflavanones (±) pterocarpans

[O]

O
R2

R1
O
isoflavones

(±)-Pterocarpan and analogues have been synthesized efficiently via the annulation of salicylaldehydes and o-methoxymethoxyl-
phenylacetylene followed by a one-pot reduction and acidic cyclization of ketones. In addition, isoflavone derivatives have been
synthesized rapidly via the annulation of salicylaldehyde and arylacetylenes followed by IBX/DMSO oxidation of the isoflavanones.

Synthesis, characterisation and antimicrobial activity of new benzo[a]phenoxazine based fluorophores pp 8347–8352
Vânia H. J. Frade, Maria J. Sousa, João C. V. P. Moura and M. Sameiro T. Gonçalves*

R-CO2H
Bze-NHCO-R H3C N
a)
Bze-NH2 Bze = H + H
N O N
R1-SO2Cl H3CH2C Cl- (CH2)3
Bze-NHSO2-R1
b)
R = azo dye, anthraquinone or pyrene
R1 = toluene

Reagents and conditions: (a) DCC/HOBt, rt; (b) 1 M NaOH/H2O, 0 °C and rt.

2-Alkylidene oxetanes by stereospecific elimination of mesylates pp 8353–8355

Paul S. Sabila and Amy R. Howell*

MsO H MsO H H H O
O t-BuOK, THF
or or
Ph Ph O
O
H H Ph Ph
 Contents / Tetrahedron Letters 48 (2007) 8253–8261 8259

3-Silyloxytetrahydrofurans via sulfoxonium ylide reactions with a-silyloxyepoxides pp 8356–8359

Paul S. Sabila, Yanke Liang and Amy R. Howell*

O O
O S I R
OTBDMS
R conditions
OTBDMS

Synthesis of new trifluoromethyl peptidomimetics with a triazole moiety pp 8360–8362

Julien Bonnamour, Julien Legros, Benoit Crousse* and Danièle Bonnet-Delpon

1. NaN3, CH3CN, r.t. N

CF3 Cl CF3 N
N
NHAc 2. Cu(OAc)2.H2O (10 mol%) NHAc
R , r.t.
74-87%

A simple and efficient synthesis of new cyclic ureas pp 8363–8365

Delphine Baumann, Khalil Bennis, Isabelle Ripoche* and Yves Troin*

O R
N
H
O O N CO2Et
CO2Et
H2N + OHC
H
1 2 O O

2 steps
9a-e 60-90% overall yield

Original N-heterocyclic ureas 9a–e were prepared efficiently from aminoketal 1 and ethyl-trans-4-oxo-buten-2-oate 2.

A versatile access to pyridazines with tethered imidazolium groups—new precursors for mono- and pp 8366–8370
binucleating NHC/pyridazine hybrid ligands
Ulrich J. Scheele, Sebastian Dechert and Franc Meyer*

R' R' R'

R' = H, Me R' R' R'
or
N N NN N N Cl
NN
N N
R' = alkyl, aryl R R R
R' 2Cl- Cl-
N
Cl Cl + R'
NN N
R R' = Cl
R' R' R' R'
R'-R' = C4H4 R' R'
N
N N NN N + R N N R
R' = Me
Cl-
8260 Contents / Tetrahedron Letters 48 (2007) 8253–8261

Solvent-free heterogeneous organocatalysis: stereoselective isomerization of a,b-ynones to pp 8371–8375

(E,E)-a,b-c,d-dienones catalyzed by polymer-supported tertiaryphosphines
Hai-Ling Liu, Huan-Feng Jiang,* Lin Xu and Hai-Ying Zhan

O O

R JJ TPP
R n-Bu
n-Bu
70 °C, 12h
1 2

Stereoselective isomerization of a,b-ynones was catalyzed by polymer-supported tertiaryphosphines under solvent-free conditions.
(E,E)-a,b-c,d-Dienones were obtained with up to 93% isolated yields when JJ-TPP was employed.

A facile method for the synthesis of substituted 2-ylidene-1,3-oxathioles from acetophenones pp 8376–8378
R. Samuel, C. V. Asokan, S. Suma, P. Chandran, S. Retnamma and E. R. Anabha*

S O
O Br
R1 1.H3CS SCH3
R2 R 3 R1 S
R 2 NaH, DMF/hexane R1 R3
O NaH, toluene O O
2. dil. HCl 48 h
H3CS S R2

Synthesis of a hexahydropyrimido[1,2-a]azepine-2-carboxamide derivative useful as an HIV integrase pp 8379–8382

inhibitor
Marco Ferrara,* Benedetta Crescenzi, Monica Donghi, Ester Muraglia, Emanuela Nizi, Silvia Pesci,
Vincenzo Summa and Cristina Gardelli

O
O N
NH 3 steps OBz 7 steps OH
O
N
N
NOH 31% 9% N N NH
N CO2 Me F
O O

From the study of naturally occurring N-allylated phenazines towards new Pd-mediated transformations pp 8383–8387
Elena Meri+or and Uwe Beifuss*
CO, Pd(OAc)2 H
N
1,10-phen, DMF
X = O, NR X
NO2

NO2
X CO, Pd(OAc)2
DMF, NEt3
O
X=O

New Pd-mediated reductive heteroannulations of N-allyl diphenylamines through Pd-catalyzed N-arylation and of O-allylethers are
reported.
 Contents / Tetrahedron Letters 48 (2007) 8253–8261 8261

Functional group selectivity in reactions of epoxides with tungsten hexachloride pp 8388–8391

Michael E. Jung* and Jennifer M. Murphy

H Z Cl Z H Z
2 eq WCl6
H CH2Cl2 H + Cl
H H Cl
O H Cl H H

The reactions of substituted cyclohexene oxides with tungsten hexachloride were carried out to learn the functional group tolerance
of this reagent. Several groups proved stable—esters, sufides, sulfones—while others were unstable—alcohols, silyl ethers, ketones.
The diaxial dichloride is usually formed although the diequatorial dichloride could also be prepared.

A convenient synthesis of linear pyridinoimidazo[1,2-a]pyridine and pyrroloimidazo[1,2-a]pyridine cores pp 8392–8395

Mounir Andaloussi,* Emmanuel Moreau, Olivier Chavignon and Jean C. Teulade

Het : Pyridine or Pyrrole

NH2 N R N
Het Het
N N N
O2N
R = CHO
R = CH=CH-N(CH3)2

*Corresponding author
Supplementary data available via ScienceDirect

COVER
This protocol directly produces chiral carboxylic esters from free carboxylic acids and racemic secondary alcohols, by utilizing the
trans-acylation process to generate mixed anhydrides from acid components and benzoic anhydride derivatives under the influence
of chiral catalysts.
Tetrahedron Letters 2007, 48, 8314–8317.
Ó 2007 I. Shiina Published by Elsevier Ltd.

Available online at www.sciencedirect.com

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ISSN 0040-4039