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Asymmetric Synthesis with Sulfur (SAS) Full Listing of Publications
2018-2015 “From Allylic Sulfoxides to Allylic Sulfenates: Fifty Years of a Never-Ending [2,3]-Sigmatropic Rearrangement”. Colomer, I.; Velado, M.; Fernández de la Pradilla, R.; Viso, A. Chem. Rev. 2018, 118, DOI: 10.1021/acs.chemrev.7b00428
RS
O
R1
R3
R2
R1
R3
R2
OSR
R1
R3
R2
HO
thiophile
naturalproducts
“Chiral Sulfur Functional Groups as Definers of the Chirality at the Metal in Ir- and Rh- Half Sandwich Complexes: A Combined CD/X-ray Study”. Avello, M. G.; Frutos, M.; de la Torre, M. C.; Viso, A.; Velado, M.; Fernández de la Pradilla, R.; Sierra, M. A.; Gornitzka, H.; Hemmert, C. Chem. Eur. J. 2017, 23, 14523−14531.
“Gold(I)-Catalyzed Cycloisomerization-Dimerization Cascade of Benzene-Tethered 1,6-Enynes”. Álvarez-Pérez, M.: Frutos, M.; Viso, A.; Fernández de la Pradilla, R.; de la Torre, M. C.; Sierra, M. A.; Gornitzka, H.; Hemmert, C. J. Org. Chem. 2017, 82, 7546−7554.
Au catalyst
O
PhH
H
H
Au catalyst
rt69-90%
Au catalyst
_10 - 0 ºC84-91%
R1
R1
R1
R1
R1
R12
3
6
1
PhCHO70-72%
R1 = H, MeO
2
“Sulfur Groups Improve the Performance of Triazole- and Triazolium-Based Interaction Units in Anion Binding”. Álvarez-Pérez, M.: Velado, M.; García-Puentes, D.; Sáez, E.; Vicent, C.; Fernández de la Pradilla, R.; Viso, A.; de la Torre, M. C.; Sierra, M. A. J. Org. Chem. 2017, 82, 3341−3346.
=X
KR:Cl < =O < =N-SO2p-Tol
Cl-
BF4S NN
NBn
Br
X
OS NN
NBn
Br
X
O
H HCl-
“Desulfinylation of Ag(I) Sulfinyl Mesoionic Carbenes: Preparation of C-Unsubstituted Au(I)−1,2,3-Triazole Carbene Complexes”. Frutos, M.; Ortuño, M. A.; Lledos, A.; Viso, A.; Fernández de la Pradilla, R.; de la Torre, M. C.; Sierra, M. A.; Gornitzka, H.; Hemmert, C. Org. Lett. 2017, 19, 822−825.
“Development of a nucleotide exchange inhibitor that impairs Ras oncogenic signaling”. Marín-Ramos, N. I.; Piñar, C.; Vázquez-Villa, H.; Martín-Fontecha, M.; González, A.; Canales, A.; Algar, S.; Mayo, P. P.; Jiménez-Barbero, J.; Gajate, C.; Mollinedo, F.; Pardo, L.; Ortega-Gutiérrez, S.; Viso, A.; López-Rodríguez, M. L. Chem. Eur. J. 2017, 23, 1676−1685.
“Gold Sulfinyl Mesoionic Carbenes: Synthesis, Structure, and Catalytic Activity”. Frutos, M.; Avello, M. G.; Viso, A.; Fernández de la Pradilla, R.; de la Torre, M. C.; Sierra, M. A.; Gornitzka, H.; Hemmert, C. Org. Lett. 2016, 18, 3570−3573.
3
“Sulfinyl-Mediated Stereoselective Overman Rearrangements and Diels−Alder Cycloadditions”. Colomer, I.; Gheewala, C.; Simal, C.; Velado, M.; Fernández de la Pradilla, R.; Viso, A. J. Org. Chem. 2016, 81, 4081−4097.
S*HO
R2
R1
R2
R1 NHP
S* Sp-Tol
O
S* =
P = COCCl3
Overman
rearrangement
54/46 - 100/0
18 examples
S*HO
R1
Overman
rearrangement
R3
S*
R3
PHN
R1
NS*
R1
O
O
R3 NHP
H
H H
Ph
> 99/120 examples
> 99/112 examples
N
O
O
Ph
“Synthesis of Enantiopure 3-Hydroxypiperidines from Sulfinyl Dienyl Amines by Diastereoselective Intramolecular Cyclization and [2,3]-Sigmatropic Rearrangement”. Simal, C.; Bates, R. H.; Ureña, M.; Giménez, I.; Koutsou, C.; Infantes, L.; Fernández de la Pradilla R.; Viso A. J. Org. Chem. 2015, 80, 7674−7692.
NH
Sp-Tol
O
PG
R3
R1R2
[2,3]-sigmatropicrearrangement
DBU-mediatedcyclization
15 examples45-83%
N
Sp-Tol
O
PG
R3
R1R2
20 examples49-88%
N
PG
R3
R1R2
14 examples42-80%
HO
**
**
NH
n-Pr
(+)-pseudoconhydrinehydrochloride
HO
·HCl
(5-6 steps f rom menthyl sulf inate)
two new stereogeniccenters are created
one-potcyclization/ [2,3]
*
N
HO
H
2014-2010 “Remote Stereocontrol in the Synthesis of Acyclic 1,4-Diols and 1,4-Aminoalcohols from 2-Sulfinyl Dienes”. Fernández de la Pradilla, R.; Velado, M.; Colomer, I.; Simal, C.; Viso A.; Gornitzka, H.; Hemmert, C. Org. Lett. 2014, 16, 5200−5203.
S
R1
R2
O
p-TolS
R1
R2
O
p-Tol
RX R1
R2
RX
OH
RXH
RXH: ROH, RNH2, R2NH
R1 = Ph, n-Bu; R2 = CH2OH, CH2OP, n-Hex
dr up to99:1
“Alkylation of α-Sulfur-Containing Carbanions”. Fernández de la Pradilla R.; Viso A. In: Gary A. Molander and Paul Knochel (eds.), Comprehensive Organic Synthesis, 2nd edition, Vol 3, Oxford: Elsevier; 2014. pp. 157−208. “Sulfoxide-Directed Enantioselective Synthesis of Functionalized Tetrahydropyridines”. Fernández de la Pradilla, R.; Simal, C.; Bates, R. H.; Viso, A.; Infantes, L. Org. Lett. 2013, 15, 4936−4939.
NH R1
Sp-Tol
OR3
R2
DBU
(dr up to 99:1)
N R1
Sp-Tol
OR3
R2
ZZ
H
Toluene, rtor
NaH/THFfor Z = Boc
56-85%
Et2NH
(dr up to 99:1)
N R1
R3
R2
Z
Toluene70-90 ºC60-80%
HO
Z = Ts, Boc(4 linear steps)
4
“Sulfinyl-Mediated Stereoselective Overman Rearrangements and Diels-Alder Cycloadditions”. Fernández de la Pradilla, R.; Colomer, I.; Viso, A. Org. Lett. 2012, 14, 3068−3071.
NS*
n-Bu
O
O
Me NHP
H
H H
()-16
H
R2
R1 NHP
S*
8a-d
(96:4 - 100:0) 90-92%
R1 = n-Bu, PhR2 = Et, Ph
(100:0) 95-97%
R2 = t-CH=CH-R3
R3 = Me, Ph
n-Bu
S*
13g,h
R3
PHN
R1
S*O
R2
5a-d / 5g,h
SHN
CCl3
BHT
Sp-Tol
OS* =
P = COCCl3
DMF100 ºC
BHTDMF
100 ºC
Ph
“An Approach to the Stereoselective Synthesis of Enantiopure Dihydropyrroles and Aziridines from a Common Sulfinyl-Sulfinamide Intermediate”. Viso, A.; Fernández de la Pradilla, R.; Ureña, M.; Bates, R.; del Águila, M. A.; Colomer, I. J. Org. Chem. 2012, 77, 525−542.
RS
HN
R1
p-Tol
O
N
R
S
p-Tol
O
Sp-Tol
O
up to 99:1dr
NP
RX
p-TolS(O)n
X = OH, Br, I
NTs
RH
Ts
BrR1 = CH=CH2
“Enantiopure 1,4-Diols and 1,4-Aminoalcohols via Stereoselective Acyclic Sulfoxide-Sulfenate Rearrangement”. Fernández de la Pradilla, R.; Colomer, I.; Ureña, M.; Viso, A. Org. Lett. 2011, 13, 2468−2471.
1) Boc2O
2) m-CPBA78%
S
O
p-TolPX
R2
3, XP = NHTs7, XP = OSiBu3
PX
R2
R1
Nuent-8
R1
OH
NuH = R2NH, RNH2R1 = H, Me; R2 = aryl, alkyl
80-90%
1
4
up to 95:5 dr
NuH, EtOH
S
10
92:8
Bu3SiO
Ph
N
OHO
Bn
Boc
11
O
N
Bn
O
OH
OHHO
Ph
H
95%
1) TFA
2) base
“Development of Chromanes as Novel Inhibitors of the Uncoupling Proteins”. Rial, E.; Rodríguez-Sánchez, L.; Aller, P.; Guisado, A.; González-Barroso, M. M.; Gallardo-Vara, E.; Redondo-Horcajo, M.; Castellanos, E.; Fernández de la Pradilla, R.; Viso, A. Chemistry & Biology 2011, 18, 264−274.
5
“Update 1 of: ,-Diamino Acids: Biological Significance and Synthetic Approaches”. Viso, A.; Fernández de la Pradilla, R.; Tortosa, M.; García, A.; Flores, A. Chem. Rev. 2011, 111, PR1−PR42 (DOI: 10.1021/cr100127y).
“Development of Molecular Probes for the Human 5-HT6 Receptor”. Vázquez-Villa, H.; González-Vera, J. A.; Benhamú, B.; Viso, A.; Fernández de la Pradilla, R.; Junquera, E.; Aicart, E.; López-Rodríguez, M. L.; Ortega-Gutiérrez, S. J. Med. Chem. 2010, 53, 7095−7106.
“Development of Fluorescent Ligands for the Human 5-HT1A Receptor”. Alonso, D.; Vázquez-Villa, H.; Gamo, A. M.; Martínez-Esperón, M. F.; Tortosa, M.; Viso, A.; Fernández de la Pradilla, R.; Junquera, E.; Aicart, E.; Martín-Fontecha, M.; Benhamú, B.; López-Rodríguez, M. L.; Ortega-Gutiérrez, S. ACS Med. Chem. Lett. 2010, 1, 249−253.
“Sulfoxide-Directed Intramolecular [4+2] Cycloadditions between 2-Sulfinyl Butadienes and Unactivated Alkynes”. Fernández de la Pradilla, R.; Tortosa, M.; Castellanos, E.; Viso, A.; Baile, R. J. Org. Chem. 2010, 75, 1517−1533.
R1
S
X
O
Ar
Y
XY
R1
S
Ar
OR2 R2
O
Ph
OHO
HO
O
Ph
OO
Sp-Tol
6
2009-2005 “Synthetic Approaches to ,-Diamino Acids”. Viso, A.; Fernández de la Pradilla, R. Amino Acids, Peptides and Proteins in Organic Chemistry, 2009, chapter 9, 411−440. Hughes A.; Ed. WILEY-VCH
XCO2H
NH2
CO2R
CO2R
X
"N "
CO2R
N
CO2R
NR R
RR
NR1
R2
NZR3
CO2R
R2HN NHR1
X Y " CO2H"
C-N bond formationC-C bond formation
R
O
OH
H2N
NH2
bcc'
Rb'
a
a
b
b
b
c
c
“Stereoselective Functionalizations of Dihydropyran-3-ols: Application to the Synthesis of Enantiopure Ethyl Deoxymonate B”. Fernández de la Pradilla, R.; Lwoff, N.; Viso, A. Eur. J. Org. Chem. 2009, 2312−2322.
S
O
HO
pTol
OTBDPS
O
OTBDPS
HO
OH
OH
46
O
OH
OH
HO
HO
CO2Et
5
8
1011
13 15
16
3042(6 steps)
“Synthesis of chiral sulfinamido-sulfonamides and their evaluation as ligands for the enantioselective ethylation of aldehydes”. Viso, A.; Fernández de la Pradilla, R.; Ureña, M. Tetrahedron 2009, 65, 3757−3766.
R
O
H R
OH
Etchiral sulfinamideCH2Cl2, rt
Et2ZnTi(OiPr)4
S:R 87:13chiral sulfinamide
NHSO2PNH
R1
R2
SR
O
NH2
SR
O
“Asymmetric Claisen Rearrangements on Chiral Vinyl Sulfoxides”. Fernández de la Pradilla, R.; Montero, C.; Tortosa, M.; Viso, A. Chem. Eur. J., 2009, 15, 697−709.
S
O
Ar
nBu
Ph S
O
nBu
Ar
HO
Ph
O
S
O
Ar
nBu
O
PhMeO2C
OHC
Ph
S
O
nBu
Ar
“Highly Diastereoselective Katsuki Jacobsen Oxidation-Epoxidation of α-Silyloxy Sulfinyl Dienes: Synthetic Applications”. Fernández de la Pradilla, R.; Castellanos, A.; Osante, I.; Colomer, I.; Sánchez, M. I. J. Org. Chem. 2009, 74, 170−181.
S
O
p-Tol
R3
R1
PO
R2O
OHR1
p-TolO2S
R2R3
2,5-trans(major isomer)
R1 = Et, i-Pr, t-Bu, n-Pent, PhR2 = H, Me; R3 = H, MeP = TBS, TES, i-Bu3Si, Bu3Si, Hex3Si
up to 99:1
O
HO
n-PentOHH H 6
6 9
Formal synthesis
1) Jacobsen2) Cyclization
7
“Highly diastereoselective Barbier allylation and iminium cyclization: a simple entry to bicyclic and tricyclic piperazinones”. Viso, A.; Fernández de la Pradilla, R.; Flores, A.; del Águila, M. A. Tetrahedron 2008, 64, 11580−11588.
N NBn
R1 CH2OP
O
N NBn
R1 CH2OP
OR2
R3OH
HN NBn
R1 CH2OP
OR2
R4
“[2,3]-Sigmatropic Rearrangements of 3-Sulfinyl Dihydropyrans: Application to the Syntheses of the Cores of ent-Dysiherbaine and Deoxymalayamicin A”. Fernández de la Pradilla, R.; Lwoff, N.; del Águila, M. A.; Tortosa, M.; Viso, A. J. Org. Chem. 2008, 73, 8929−8941.
S
RO
HO
p-Tol
O
HO
R O
O
R
NH
OH
O
O
OO
N
H
H
MeO
O
8e 24e ent-16(6 steps)R = (CH2)2OTBDPS
“Highly Diastereoselective Addition of Lithio Vinyl Sulfoxides to N-Sulfinimines: An Entry to Enantiopure 3-Sulfinyl-2,5-cis-dihydropyrroles”. Viso, A.; Fernández de la Pradilla, R.; Ureña, M.; Colomer, I. Org. Lett. 2008, 10, 4775−4778.
RS
HN
R'
p-Tol
O
N
R
S
p-Tol
O
Sp-Tol
O
R = aryl, alkyl R' = alkyl, vinyl
93-98% yield, up to 99:1 dr NTs
RBr
SO
p-Tol
NTs
ROH
Ts
“Synthesis of Ethyl Deoxymonate B”. Fernández de la Pradilla, R.; Lwoff, N. Synfacts 2008, 10, 1015. “Sulfur-Directed Enantioselective Synthesis of Functionalized Dihydropyrans”. Fernández de la Pradilla, R.; Tortosa, M.; Lwoff, N.; del Águila, M. A.; Viso, A. J. Org. Chem. 2008, 73, 6716−6727.
n-Bu
S
OH
O
p-Tol
8b(4 steps)
O
SO2p-Tol
n-Bu
H
20b
O
n-Bu
n-Bu
OH
OH
2 steps
50a
oxidation
O
S
n-Bu
p-Tol
OH
Base-mediatedcyclization
10b
“Synthesis of enantiopure ethyl deoxymonate B from allylic sulfinyl dihydropyrans”. Fernández de la Pradilla, R.; Lwoff, N. Tetrahedron Lett. 2008, 49, 4167−4169.
8
“The medicinal chemistry of agents targeting monoacylglycerol lipase” Viso, A.; Cisneros, J. A.; Ortega-Gutiérrez, S. Current Topics in Medicinal Chemistry 2008, 8, 231−246.
NC5H11
OHO
OC5H11
OHO
(2)
OH
(1)
OC5H11
NH2
O
(3)
OC5H11
OH
(4)
OH
H
“Formal synthesis of ent-dysiherbaine from sufinyl dihydropyrans by sigmatropic rearrangement and tethered aminohydroxylation”. Fernández de la Pradilla, R.; Lwoff, N.; Viso, A. Tetrahedron Lett. 2007, 48, 8141−8144.
S
RO
HO
p-Tol
O
HO
R O
O
R
NHOH
O
O
OO
N
H
H
MeO
O
18 20 ent-216 (6 steps)R = (CH2)2OTBDPS
“Katsuki-Jacobsen oxidation-epoxidation of α-silyloxy sulfinyl dienes. Application to the formal synthesis of (6S,7S,9R,10R)-6,9-epoxynonadec-18-ene-7,10-diol”. Fernández de la Pradilla, R.; Castellanos, A. Tetrahedron Lett. 2007, 48, 6500−6504.
Sn-Pent
Bu3SiO O
p-TolSO2p-Tol
n-Pent
Bu3SiO
OO
BzO
n-PentH
OH H
11a (3 steps) 14a90:10
17
Jacobsen
“Synthesis of enantiopure vicinal diaminoesters and ketopiperazines from N-sulfinylimidazolidines”. Viso, A.; Fernández de la Pradilla, R.; Flores, A.; García, A. Tetrahedron 2007, 63, 63, 8017−8026.
N NH
R1 CO2Me
Ar
SpTol
O
R1CO2Me
NHP1
NHP2
P2N NP1
CO2MeR1
O
“Sulfur Participation in [3,3]-Sigmatropic Rearrangements”. Fernández de la Pradilla, R.;Tortosa, M.; Viso, A. Top. Curr. Chem. 2007, 275, 103−129. “Highly diastereoselective Staudinger reaction on 5,6-dihydropyrazin-2-(1H)-ones. Synthesis of enantiopure fused oxopiperazino--lactams”. Viso, A.; Fernández de la Pradilla, R.; Flores, A. Tetrahedron Lett. 2006, 47, 8911−8915.
N N
O
R1 OP
Bn N N
O
R1 OP
BnO
R2H
HN N
O
R1 OH
BnMeO2C
R2H
9
“Sulfur-mediated Synthesis of Substituted Tetrahydrofurans: Application to the Synthesis of Goniofufurone”. Fernández de la Pradilla, R.; Fernández, J.; Viso, A.; Fernández, J.; Gómez, A. Heterocycles 2006, 68, 1579−1584.
SO2p-TolOH
OPO
t-BuO2C
SO2p-TolOO
OP
CO2t-Bu
O
OP
O
O
OH
HH
5(5 steps)
4 9
Triton BMeOH
MgBr2
P = TBDPS
O
O O
Ph
HO
H
H
H
HO
(+)-goniofufurone, 1
“Synthesis of Tetrahydrofurfurylamines Related to Muscarine”. Fernández de la Pradilla, R.; Manzano, P.; Viso, A.; Fernández, J.; Gómez, A. Heterocycles 2006, 68, 1429−1442.
O
p-F-Ph
OH
OH
O
p-F-Ph
NR1R2
OHO
p-F-Ph
NR1R2
NR3R4
“Nucleophilic epoxidation of -alkoxy dienyl sulfoxide derivatives”. Fernández de la Pradilla, R.; Buergo, M. V.; Montero, C.; Viso, A. Tetrahedron 2006, 62, 2684−2692.
SR3
OP
R4
R3
OP
R4
O
P = H, TBDMSn = 1, 2R3, R4 = alkyl
O
p-Tol
( )n
SO
p-Tol
( )nMOO-tBu
“Metal-Catalyzed Oxidation and Epoxidation of α-Hydroxy Vinyl and Dienyl Sulfoxides”. Fernández de la Pradilla, R.; Castellanos, A.; Fernández, J.; Lorenzo, M.; Manzano, P.; Méndez, P.; Priego, J.; Viso, A. J. Org. Chem. 2006, 71, 1569−1575.
R1
R2
HO
S
O
R3 R1
R2
HO
SO2R3
O
anti
t-BuOOH
VO(acac)2C6H6, rt54-91%
SO2p-TolPO
O O
PhSO2p-Tol
O
Ph
HO
O3
88%
SO2p-TolAcO
Ph
OH
O
SO2p-TolAcO
Ph
OHO
O353%
BF3·OEt2, 72%
SnBu3
P = H, Ac
80:20
“Synthesis of Highly Substituted Enantiopure Piperazines and Ketopiperazines from Vicinal N-Sulfinyl Diamines”. Viso, A.; Fernández de la Pradilla, R.; Flores, A.; García, A.; Tortosa, M.; López-Rodríguez, M. L. J. Org. Chem. 2006, 71, 1442−1448.
CH2OH
NHBn
HN pTol
O
SHNNBn
OH
HN NBn
O
OP
N NBn
O
OP
P = TBDMS
10
“Reductive Cleavage of Tetrahydrofuryl Sulfur-Substituted Oxiranes: Application to the Formal Synthesis of Kumausyne and Kumausallene”. Fernández de la Pradilla, R.; Alhambra, C.; Castellanos, A.; Fernández, J.; Manzano, P; Montero, C.; Ureña, M.; Viso, A. J. Org. Chem. 2005, 70, 10693−10700.
O
S
OP
R
O
3a-e, S = SOpTol4a-e, S = SO2pTol
(PhSe)2
NaBH4EtOH
O
OP
ROH
16
O
OP
ROH
17
O
OP
ROMgI2
15a22a,c
Et2O
60:40-87:13
O
AcO
Et
Br(–)-trans-Kumausyne, 1
H HO Et
OC
H H
(–)-Kumausallene, 2Br
Br
H
H
H
“,-Diamino Acids: Biological Significance and Synthetic Approaches”. Viso, A.; Fernández de la Pradilla, R.; García, A.; Flores, A. Chem. Rev. 2005, 105, 3167−3196.
“Highly Diastereoselective Diels-Alder Reactions with Enantiopure Sulfinyl-Substituted 1-Hydroxymethyldienes”. Fernández de la Pradilla, R.; Montero, C.; Tortosa, M.; Viso, A. Chem. Eur. J. 2005, 11, 5136−5145.
NPM
orPTAD
X = CH, N; Y = SOpTol, SO2pTol,
-endo
NPM
orPTAD
-endo
X
X
Y
R1
N
O
O
HO
Ph
R2
SO2pTol
R1
HO R2
S
R1
HO R2
O
pTol
“Synthesis of Functionalized Tetrahydrofurans from Hydroxy Sulfinyl Dienes”. Fernández de la Pradilla, R.; Castellanos, A.; Ureña, M.; Viso, A. Phosphorus, Sulfur and Silicon 2005, 180, 1461−1462. “Highly Diastereoselective [3+2] Cycloadditions Between Non-Racemic p-Tolylsulfinimines and Iminoesters: An efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols”. Viso, A.; Fernández de la Pradilla, R.; García, A.; Guerrero-Strachan, C.; Alonso, M.; Tortosa, M.; Flores, A.; Lwoff, N.; López-Rodríguez, M. L.; Martínez-Ripoll, M.; Fonseca, I.; André, I.; Rodríguez, A. Phosphorus, Sulfur and Silicon 2005, 180, 1229−1234. “Base-Induced Enantioselective Synthesis of Sulfinyl Dihydropyrans”. Fernández de la Pradilla, R.; Tortosa, M. Phosphorus, Sulfur and Silicon 2005, 180, 1217−1222. “Involvement of Cannabinoids in Cellular Proliferation”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Díaz-Laviada, I. Mini-Reviews in Medicinal Chemistry 2005, 5, 97−106.
11
“Activation of the endocannabinoid system as therapeutic approach in a murine model of multiple sclerosis”. Ortega-Gutiérrez, S.; Molina-Holgado, E.; Arévalo-Martín, A.; Correa, F.; Viso, A.; López-Rodríguez, M. L.; Di Marzo, V.; Guaza, C. The FASEB Journal 2005, 19, 1338−1340. “Synthesis and Structure-Activity Relationships of a New Model of Arylpiperazines. 8. Computational Simulation of Ligand-Receptor Interaction of 5-HT1AR Agonists with Selectivity over -Adrenoceptors”. López-Rodríguez, M. L.; Morcillo, M. J.; Fernández, E.; Benhamú, B.; Tejada, I.; Ayala, D.; Viso, A.; Campillo, M.; Pardo, L.; Delgado, M.; Manzanares, J.; Fuentes, J. A. J. Med. Chem. 2005, 48, 2548−2558.
2004 “Sulfoxide-Controlled SN2’ Displacements between Cuprates and Vinyl and Alkynyl Epoxy Sulfoxides”. Fernández de la Pradilla, R.; Viso, A.; Castro, S.; Fernández, J.; Manzano, P.; Tortosa, M. Tetrahedron 2004, 60, 8171−8180.
SO
p-Tol
RO
R1
"R2Cu" "R3Cu"
SO
p-Tol
R OH
R1
R2
HS
O
p-Tol
R
R1
R2
R3
“Sulfoxide-Directed Enantioselective Synthesis of Functionalized Dihydropyrans”. Fernández de la Pradilla, R.; Tortosa, M. Org. Lett. 2004, 6, 2157−2160.
O
S
R2
O
p-Tol
R2
S
OH
O
p-Tol LDA
60-94%R1
R3H
R3
R1 O
SO2p-Tol
Ph
HO
“Sulfur-Directed Synthesis of Enantiopure Hydroxy 2-Sulfinyl Butadienes”. Fernández de la Pradilla, R.; Buergo, M. V.; Martínez, M. V.; Montero, C.; Tortosa, M.; Viso, A. J. Org. Chem. 2004, 69, 1978−1986.
SAr
R2
HO
Cl
R
SAr
R2
R3
Z/E
17
OHO O
SAr
R2
HO
R
4 21
E/E
OCl
SAr
R
O
R2
HOTHF THF
KO-t-Bu KO-t-Bu
“Synthesis and Structure-Activity Relationships of a New Model of Arylpiperazines. 7. Study of the Influence of Lipophilic Factors at the Terminal Amide Fragment on 5-HT1A Affinity/Selectivity”. López-Rodríguez, M. L.; Ayala, D.; Viso, A.; Benhamú, B.; Fernández de la Pradilla, R.; Zarza, F.; Ramos, J. A. Bioorg. Med. Chem. 2004, 12, 1551−1557.
NN
O
( )n
NN
O
R1
n = 1, 4R1 = Me, Et, Pr, iPr,
Bu, iBu, Pn, iPn,Hex, Hept, allyl
MeO
“Fine-Tuned Aminal Cleavage: A Concise Route to Differentially Protected Enantiopure syn-,-Diamino Esters”. Viso, A.; Fernández de la Pradilla, R.; López-Rodríguez, M. L.; García, A.; Flores, A.; Alonso, M. J. Org. Chem. 2004, 69, 1542−1547.
N NH
Ar
CO2MeR
S
O
p-Tol
R1R
CO2Me
NH
H2N R1
Sp-Tol
O
H3PO4/THF
12
“Characterization of an anandamide degradation system in prostate epithelial PC-3 cells: synthesis of new transporter inhibitors as tools for this study”. Ruiz-Llorente, L.; Ortega-Gutiérrez, S.: Viso, A.; Sánchez, M. G.; Sánchez, A. M.; Fernández, C.; Ramos, J. A.; Hillard, C.; Lasunción, M. A.; López-Rodríguez, M. L.; Díaz-Laviada, I. Br. J. Pharmacol. 2004,141, 457−467. “Comparison between anandamide transport in FAAH wild type and knockout neurons: evidence for contributions by both FAAH and CB1 receptor to anandamide uptake”. Ortega-Gutiérrez, S.; Hawkins, G. E.; Viso, A.; López-Rodríguez, M. L.; Cravatt, B. F. Biochemistry 2004, 43, 8184−8190.
2003 “Nucleophilic Epoxidation of ’-Hydroxy Dienyl Sulfoxides”. Fernández de la Pradilla, R.; Manzano, P.; Montero, C.; Priego, J.; Martínez-Ripoll, M.; Martínez-Cruz, L. A. J. Org. Chem. 2003, 68, 7755−7767.
HOS*
R3
4
HOS*
R3
O
12
O
S*R3
OH16
O
S*R3
OH
O
18
KOO-t-Bu
THF
S* = S
O
p-Tol “Sulfoxide-Directed Thermal Intramolecular [4+2] Cycloadditions between 2-Sulfinyl Butadienes and Unactivated Alkynes”. Fernández de la Pradilla, R.; Baile, R.; Tortosa, M. Chem. Commun. 2003, 2476−2477.
R2
XY
SO
X
Y
R2
SO
p-Tol
R1 R1
p-Tol
X
Y
R2
SO
p-Tol
R1
+
3a-3g (73-98) 4a-4g (27-2)2a-2g
rt-90 ºC
70-95%
R1 = H, CH3R2 = n-Bu, PhX = O, NTs, C(SO2Ph)2
Y = CH2, (CH2)2, CO “Nucleophilic Epoxidation of -Hydroxyvinyl Sulfoxide Derivatives”. Fernández de la Pradilla, R.; Buergo, M. V.; Manzano, P.; Montero, C.; Priego, J.; Viso, A.; Cano, F. H.; Martínez-Alcázar, M. P. J. Org. Chem. 2003, 68, 4797−4805.
R
S
O
ArPO
R
S
O
ArPO
Ot-BuOOM
THF
“Highly Diastereoselective [3+2] Cycloadditions between Non-racemic p-Tolylsulfinimines and Iminoesters: an Efficient Entry to Enantiopure Imidazolidines and Vicinal Diaminoalcohols”. Viso, A.; Fernández de la Pradilla, R.; García, A.; Guerrero-Strachan, C.; Alonso, M.; Tortosa, M.; Flores, A.; Martínez-Ripoll, M.; Fonseca, I.; André, I.; Rodríguez, A. Chem. Eur. J. 2003, 9, 2867−2876.
R1
NS
O
pTolR5HN NHR4
R1R2
NN
SpTol
R1
MeO2C
Ph
R2
O
H
OR5 “Design and synthesis of S-(−)-2-[[4-(napht-1-yl)piperazin-1-yl]methyl]-1,4-dioxoperhydropyrrolo[1,2-a]pyrazine (CSP-2503) using computational simulation. A 5-HT1A receptor agonist”. López-Rodríguez, M. L.; Morcillo, M. J.; Fernández, E.; Benhamú, B.; Tejada, I.; Ayala, D.; Viso, A.; Olivella, M.; Pardo, L.; Delgado, M.; Manzanares, J.; Fuentes, J. A. Bioorg. Med. Chem. Lett. 2003, 13, 1429−1432. “Design, Synthesis, and Biological Evaluation of New Inhibitors of the Endocannabinoid Uptake: Comparison with Effects on Fatty Acid Amidohydrolase”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Fowler, C. J.; Tiger, G.; de Lago, E.; Fernández-Ruiz, J.; Ramos, J. A. J. Med. Chem. 2003, 46, 1512−1522.
13
“Design, synthesis and biological evaluation of new endocannabinoid transporter inhibitors”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Fowler, C. J.; Tiger, G.; de Lago, E.; Fernández-Ruiz, J.; Ramos, J. A. Eur. J. Med. Chem. 2003, 38, 403−412. “VR1 Receptor Modulators as Potential Drugs for Neuropatic Pain”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S. Mini-Reviews in Med. Chem. 2003, 3, 729−748. “Inhibition of Fatty Acid Amidohydrolase, the Enzyme Responsible for the Metabolism of the Endocannabinoid Anandamide, by Analogues of Arachidonyl-serotonin”. Fowler, C. J.; Tiger, G.; López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Ramos, J. A. Journal of Enzyme Inhibition and Medicinal Chemistry 2003, 18, 225−231.
2002 “Nucleophilic Epoxidation of ’-Hydroxy Vinyl Sulfoxides”. Fernández de la Pradilla, R.; Fernández, J.; Manzano, P.; Méndez, P.; Priego, J.; Tortosa, M.; Viso, A.; Martínez-Ripoll, M.; Rodríguez, A. J. Org. Chem. 2002, 67, 8166−8177.
SR1
OH
t-BuOOM SR1
HO
SO2p-TolR1
HO
R3 R3 R3
O Op-Tol
OO
p-Tol
“Sulfinyl-Mediated Chirality Transfer in Diastereoselective Claisen Rearrangements”. Fernández de la Pradilla, R.; Montero, C.; Tortosa, M. Org. Lett. 2002, 4, 2373−2376.
S Ar
nBu
PhO
S
nBuHO
Ph
Ar = 1-Napht(2-OMe)
80%
SpTol
nBu
O
Ph
CO2Me
SpTol
Ph
nBuH
O79%
Ar
OO O
O
“Synthesis of Enantiopure 1-Benzyl-2,3-disubstituted Piperazines from Enantiopure p-Toluenesulfinimines”. Viso, A.; Fernández de la Pradilla, R.; López-Rodríguez, M. L.; García, A.; Tortosa, M. Synlett 2002, 755−758.
R1 = aromatic, aliphatic; R2 = H, TBDMS; R3 = p-TolSO, H; R4 = R5 = H, O
R3N NBn
O
OR2R1
R4 R5
NH NHBn
R1
S
O
p-Tol
OR2
R3NNBn
OR2R1
NS
O
p-Tol
R1
“UCM707, a potent and selective inhibitor of endocannabinoid uptake, potentiates hypokinetic and antinociceptive effets of anandamide”. de Lago, E.; Fernández-Ruiz, J.; Ortega-Gutiérrez, S.; Viso, A.; López-Rodríguez, M. L.; Ramos, J. A. Eur. J. Pharmacol. 2002, 449, 99−103. “Benzimidazole Derivatives. 3. 3D-QSAR/CoMFA Model and Computational Simulation for the Recognition of 5-HT4 Receptor Antagonists”. López-Rodríguez, M. L.; Murcia, M.; Benhamú, B.; Viso, A.; Campillo, M.; Pardo, L. J. Med. Chem. 2002, 45, 4806−4815. “Arylpiperazine Derivatives Acting at 5-HT1A Receptors”. López-Rodríguez, M. L.; Ayala, D.; Benhamú, B.; Morcillo, M. J.; Viso, A. Current Medicinal Chemistry 2002, 9, 443−469. “Endocannabinoid Transporter Inhibitors”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Fernández-Ruiz, J.; Ramos, J. A. Current Medicinal Chemistry-CNS Agents 2002, 2, 129−141. “5-HT4 Receptor Antagonists: Structure-Affinity Relationships and Ligand-Receptor Interactions”. López-Rodríguez, M. L.; Benhamú, B.; Morcillo, M. J.; Murcia, M.; Viso, A.; Campillo, M.; Pardo, L. Current Topics in Medicinal Chemistry 2002, 2, 625−641. “Inactivación de los Endocannabinoides: Sistema de Terminación”. López-Rodríguez, M. L.; Ortega-Gutiérrez, S; Viso, A. Guia Básica sobre los Cannabinoides, 2002, Capítulo 5, pag.49−62.
14
2001
“Synthesis of Enantiopure Tetrahydrofurans from Sulfinyl Dienes: Application to the Synthesis of (+)-trans-Kumausyne and (+)-Kumausallene”. Fernández de la Pradilla, R.; Viso, A. Recent Res. Devel. in Org. & Bioorg. Chem. 2001, 4, 123−132. “3D-QSAR/CoMFA and Recognition Models of Benzimidazole Derivatives at the 5-HT4 Receptor”. López-Rodríguez, Murcia, M.; M. L.; Benhamú, B.; Viso, A.; Campillo, M.; Pardo, L. Bioorg. Med. Chem. Lett. 2001, 11, 2807−2811. “Study of the bioactive conformation of novel 5-HT4 receptor ligands: influence of an intramolecular hydrogen bond”. López-Rodríguez, M. L.; Benhamú, B.; Viso, A.; Murcia, M.; Pardo, L. Tetrahedron 2001, 57, 6745−6749. “Design, Synthesis and Biological Evaluation of Novel Arachidonic Acid Derivatives as Highly Potent and Selective Endocannabinoid Transporter Inhibitors”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Lastres-Becker I.; González, S.; Fernández-Ruiz, J.; Ramos, J. A. J. Med. Chem. 2001, 44, 4505−4508. “Nuevas tendencias en la utilidad terapéutica de los cannabinoides”. López-Rodríguez, M. L.; Viso, A.; Ortega-Gutiérrez, S.; Fernández-Ruiz, J.; Ramos, J. A. An. Quim. 2001, 97, 14−21.
2000 “Sulfur-Directed Asymmetric Synthesis of Imidazolidines and 1,2-Diamines from Enantiopure Sulfinimines”. Viso, A.; Fernández de la Pradilla, R. Recent Res. Devel. in Organic Chem. 2000, 4, 327−334. “Sulfoxide Controlled SN2’ Displacements between Cyanocuprates and Epoxy Vinyl Sulfoxides”. Marino, J. P.; Anna, L. J.; Fernández de la Pradilla, R.; Martínez, M. V.; Montero, C.; Viso, A. J. Org. Chem. 2000, 65, 6462−6473.
S
R1
O
p-Tol
R2
OS
R1
O
p-Tol
R2 OH
R
S
R1
O
p-Tol
R2
O S
R1
O
p-Tol
R2 OH
RANTI SN2' SYN SN2'
RCuCNLi RCuCNLi
“Highly Diastereoselective Dihydroxylation of cis-Substituted Sulfonyl Vinyl Oxiranes”. Fernández de la Pradilla, R.; Méndez, P.; Viso, A. Tetrahedron Lett. 2000, 41, 2871−2874.
PhSO2p-Tol
O
1. OsO4Me3NO
2. Ac2OEt3N
PhSO2p-Tol
O
AcO
AcO
PO PO
P = H, Bn, Ac
85:15-100:0
“Pd (0) Amination of Benzimidazoles as an Efficient Method towards New (Benzimidazolyl)piperazines”. López-Rodríguez, M. L.; Benhamú, B.; Ayala, D.; Rominguera, J. L.; Murcia, M.; Ramos, J. A.; Viso, A. Tetrahedron 2000, 56, 3245−3253.
1999 “Lewis Acid Catalyzed Condensation between Glycine Iminoester Enolates and p-Tolylsulfinimines”. Viso, A.; Fernández de la Pradilla, R.; García, A.; Alonso, M.; Guerrero-Strachan, C.; Fonseca, I. Synlett 1999, 1543−1546.
Ar
N
OMe
N
Ar1
NN
S*
ArCO2Me
Ar1
H+S*
O
1. LDA2. BF3
.OEt23. 0.1 M CHCl3
53-75%
76:24-90:10
NHNH
S*
Ar
Ph
OH
LiAlH4Et2O
63-71%
S* = SO
p-Tol
15
“Highly Stereoselective Metal-Catalyzed Epoxidation of Hydroxy Vinyl Sulfones”. Fernández de la Pradilla, R.; Méndez, P.; Priego, J.; Viso, A. J. Chem. Soc., Perkin Trans. 1 1999, 1247−1249.
S
R2
HO
R1
R3
O
SO2R3
R2
HO
R1
OO O
SO2p-TolButOOH
VO(acac)2
54-76%for R1 = Ph,R2 = vinyl,R3 = p-Tol
Ph
HO5 (88%)
O3
“Benzimidazole Derivatives. Part I: Synthesis and Structure- Activity Relationships of New Benzimidazole-4-carboxamides and Carboxylates as Potent and Selective 5-HT4 Receptor Antagonist”. López-Rodríguez, M. L.; Benhamú, B.; Viso, A.; Morcillo, M. J.; Murcia, M.; Orensanz, L.; Alfaro, M. J.; Martín, M. I. Bioorg. Med. Chem. 1999, 7, 1333−1343. “Synthesis of New (benzimidazolyl)piperazines with Affinity for the 5-HT1A Receptor via Pd(0) Amination of Bromobenzimidazoles”. López-Rodríguez, M. L.; Viso, A.; Benhamú, B.; Rominguera, J. L.; Murcia, M. Bioorg. Med. Chem. Lett. 1999, 9, 2339−2342.
1998 “Highly Stereoselective Nucleophilic Epoxidation of Simple Vinyl Sulfoxides”. Fernández de la Pradilla, R.; Viso, A. Recent Res. Devel. in Organic Chem. 1998, 2, 343−349. “A Novel Sulfoxide-Directed Route to Enantiopure Tetrahydrofurans: Application to the Expedient Formal Synthesis of (+)-trans-Kumausyne and (+)-Kumausallene”. Fernández de la Pradilla, R.; Montero, C.; Priego, J.; Martínez-Cruz, L. A. J. Org. Chem. 1998, 63, 9612−9613.
O OS*
R
OH
S*HO
R
O
O
OH
OTBDPS
S*=
Twosteps
Sp-Tol
OA, ent-trans-KumausyneB, ent-Kumausallene
A
B
KOO-t-Bu
“Highly Stereoselective Nucleophilic Epoxidation of Simple Vinyl Sulfoxides”. Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Martín-Ortega, M.; Priego, J.; Viso, A.; Rodríguez, A.; Fonseca, I. J. Org. Chem. 1998, 63, 4954−4966.
R3 R4
R2
Yield = 61-94%; de = 55-96%M = Li, Na, K
S
O
R3 R4
R2
O
S
O
R3 R4
R2
O4 equiv MOO-t -Bu
THF, 0 ºC
20 min-3 days
+S
O
R1 R1
R1 = p-Tol, t-Bu
R1
“Sulfinyl versus Allylic Stereocontrol in Diels-Alder Cycloadditions of Hydroxy 2-Sulfinyl Butadienes”. Fernández de la Pradilla, R.; Montero, C.; Viso, A. Chem. Commun. 1998, 409−410.
S
n-Pr
HO n-Bu
S
O
O
H
O
PhHN
n-BuHa
n-Pr
HbO
p-Tol
O
p-TolSO2p-Tol
n-Pr
HO n-Bu
SO2p-Tol
O
O
H
H
O
PhHN
n-Bu
n-PrN
O
O
Ph N
O
O
Ph
16
1997 “Synthesis and Diastereoselective Complexation of Enantiopure Sulfinyl Dienes: The preparation of Sulfinyl Iron(0) Dienes”. Paley, R. S.; de Dios, A.; Estroff, L. A.; Lafontaine, J. A.; Montero, C.; McCulley, D. J.; Rubio, M. B.; Ventura, M. P.; Weers, H. L.; Fernández de la Pradilla, R.; Castro, S.; Dorado, R.; Morente, M. J. Org. Chem. 1997, 62, 6326−6343.
“Sulfur-Directed Asymmetric 1,3-Dipolar Cycloadditions of Azomethine Ylides with Enantiopure Sulfinimines”. Viso, A.; Fernández de la Pradilla, R.; Guerrero-Strachan, C.; Alonso, M.; Martínez-Ripoll, M.; André, I. J. Org. Chem. 1997, 62, 2316−2317.
Ar
N
OMe
RN
Ph
LiN
N
Sp-Tol
ArMeO2C
Ph
R
O
H+
SO
p-Tol
O
H2NNH2
PhPh
OH
53-80%90-94% de
“Enantioselective Carbon-Carbon Bond Formation via SN2’ Displacements of Acyclic Allylic Mesylates”. Marino, J. P.; Viso, A.; Lee, J.-D.; Fernández de la Pradilla, R.; Fernández, P.; Rubio, M. B. J. Org. Chem. 1997, 62, 645−653.
R1 Sp-Tol
R
(O)nMsOSO2p-TolS
O
p-Tol"R2Cu""R2Cu"
R2 R2
R1
R1
RRn = 1 n = 2
de = 82-86%de = 88%
1996 “Diastereoselective Formation of an [-(1Z)-(Sulfinyldiene)]Iron(0) Tricarbonyl Complex. Diastereoselective Allylation of the Derived Iron Dienal”. Paley, R. S.; Rubio, M. B.; Fernández de la Pradilla, R.; Dorado, R.; Hundal, G.; Martínez-Ripoll, M. Organometallics 1996, 15, 4672−4674.
S*
EtO
EtOFe(CO)3
S*
O
H
Sp-Tol
HO
Fe(CO)3
S*S* =
*
O 1) Fe(CO)5
2) Amberlite
SnBu3
BF3·OEt2
“Sulfoxide-Controlled SN2’ Displacements between Cyanocuprates and Epoxy Vinyl Sulfoxides”. Marino, J. P.; Anna, L. J.; Fernández de la Pradilla, R.; Martínez, M. V.; Montero, C.; Viso, A. Tetrahedron Lett. 1996, 37, 8031−8034.
R1
Sp-Tol
O
R2O
R1
Sp-Tol
O
R
R2 OH
R1
Sp-Tol
O
R2 O
R1
Sp-Tol
O
R
R2 OH
6 equiv RCuCNLiEt2O, –78 ºC to rt
6 equiv RCuCNLiEt2O, –78 ºC to rt
68-78% ; de = 70-100% 70-91% ; de = 86-100%ANTISYN
“Stereoselective Nucleophilic Epoxidation of Vinyl Sulfoxides: A Novel Route to Enantiopure Sulfinyl Oxiranes”. Fernández de la Pradilla, R.; Castro, S.; Manzano, P.; Priego, J.; Viso, A. J. Org. Chem. 1996, 61, 3586−3587.
R3 R4
R2
Yield = 70-84%; de = 55-96%M = Li, Na
S
O
R3 R4
R2
O
S
O
R3 R4
R2
O4 equiv MOOt -Bu
THF, 0 ºC20 min-4 h
+S
O
R1 R1
R1 = p-Tol, t-Bu
R1
17
“Highly Stereocontrolled Formal Synthesis of Brassinolide via Chiral Sulfoxide-Directed SN2’ Reactions”. Marino, J. P.; de Dios, A.; Anna, L. J.; Fernández de la Pradilla, R. J. Org. Chem. 1996, 61, 109−117.
BrassinolideO
OH
OH
HO
HO
OH
HH
H
“Tetra-n-butylammonium Acetate”. Fernández de la Pradilla, R.; Viso, A. Encyclopedia of Reagents for Organic Synthesis Wiley, 1996.
1995 “Stereocontrolled Synthesis of Enantiomerically Pure 2-Dienyl Sulfoxides via Palladium-Catalyzed Coupling Reactions”. Paley, R. S.; Weers, H. L.; Fernández, P.; Fernández de la Pradilla, R.; Castro, S. Tetrahedron Lett. 1995, 36, 3605−3608.
NIS
NIS
n-Bu3Sn S
O
p-Tol
n-Bu
S
O
p-Tol
n-Bu
IS
O
p-Tol
n-Bu
RS
O
p-Toln-Bu
n-Bu3Sn S
O
p-Tol S
O
p-TolSYNHydrostannylation
I S
O
p-Toln-Bu n-Bu n-Bu
Pd2(dba)3,Ph3As, BHT
R = H, Ph
n-Bu3SnHHex
ANTIHydrostannylation n-Bu3SnH
2% Pd(Ph3P)4Tol
“Base-Induced Bridge Cleavage of 1,5-Dimethyl-7-oxabicyclo[2.2.1]hept-5-ene systems”. Arjona, O.; Conde, S.; Plumet, J.; Viso A. Tetrahedron Lett. 1995, 36, 6157-6158.
1994 “A Stereodivergent Access to Naturally Occurring Aminocarbasugars from (Phenylsulfonyl)-7-oxabicyclo[2.2.1]heptane Derivatives. Total Synthesis of Penta-N,O-acetyl-(±)-Validamine and its C1 and C2 Stereoisomers”. Aceña, J. L.; Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 6419−6424.
OH
BnO OBn
OH
BnO OBn
PhSO2O
OTBS
TBSO OTBS
OTBS
TBSO OTBS
PhSO2OLiOOt-Bu
THF, 80%
single isomer
LiOOt-BuTHF, 92%
1
J1,2 = 6.8J1,6 = 9.8
2 6
J1,2 = 2.7J1,6 = 2.7
PhSO2PhSO2
MgBr2·OEt2
OH
BnO OBn
PhSO2O
OH
BnO OBn
O
Br
OH
HO OH
NH2HO
1) NaN32) LiAl(O-t-Bu)3H
3) H2, Pd/CEPI-VALIDAMINE
80%
“Intramolecular [4+2] Cycloaddition Reactions of Conjugated Enynes”. Danheiser, R. L.; Gould, A. E.; Fernández de la Pradilla, R.; Helgason, A. L. J. Org. Chem. 1994, 59, 5514−5515.
AlCl3 MeSO3H
OOMe
OOMe
O O
18
“Sulfone Directed Alkylative Bridge Cleavage of Oxabicyclic Vinyl Sulfones with Organolithium Reagents”. Arjona, O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1994, 59, 3906−3916.
RLi RLiO
OHR
PhSO2 OBnPhSO2OBn
O
OHR OBn
PhSO2
OBn
R = Me, n-Bu, allyl, 2-propenyl 64-81% 69-82%R = Me, 1-hexynyl, 2-furyl
PhSO2
88%O
OHMe OBn
PhSO2
OBn
OMOM OMOM
MeLi
PhSO2
“Kinetic Resolution of 2,5-Disubstituted Pyrrolines via Asymmetric Hydrogenation with a Chiral Titanocene Complex”. Viso, A.; Lee, N.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 9373-9374.
1993 “Síntesis total de carba- y amino carba- azúcares a partir de derivados de (fenilsulfonil)-7-oxabiciclo [2.2.1]heptano”. Aceña, J. L.; Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. An. Quím. 1993, 89, 145−148. “Synthesis of Endo or Exo Norbornenic Lactones via Highly Diastereoselective Lactonization of Bicyclic Vinyl Sulfoxides”. Arjona, O.; Fernández, P.; Fernández de la Pradilla, R.; Morente, M.; Plumet, J. J. Org. Chem. 1993, 58, 3172−3175.
SO
Tol
OSTol
H
OO
STol
H
O
(86 : 14)
SO
Tol
OO
H
STolO
O
H
STol(91 : 9)
“Stereocontrolled Synthesis of Enantiomerically Pure Dienyl Sulfoxides via Palladium-Catalyzed Coupling Reactions”. Paley, R. S.; de Dios, A.; Fernández de la Pradilla, R. Tetrahedron Lett. 1993, 34, 2429−2432.
SI
R
O
p-TolS
p-Tol
O(vinyl)Snn-Bu3
Pd(CH3CN)2Cl2DMF, rt, 10 min
R
1992 “Osmium-Mediated Asymmetric Synthesis of Glycosyl-myo-inositols from Oxanorbornanes”. Arjona, O.; Candilejo, A.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J. J. Org. Chem. 1992, 57, 6097−6099.
OR3
OR1
O OR2
O
O
R1O
O
R3O
OR1
OR2O
OO
OR1O
O
O
R1O
HO1,4 - GPI
(±)-4 R1 = Bn
O-P
OR1
O OR2
1,6 - GPI
R3O
OR1
OR2O
GLYCOSYL CONDURITOL B
= Glycoside
OH
HO
OH
O-P
14
16
G
G
G
G
GG
G
19
“Synthesis of Enantiomerically Pure (Z)-2-Haloalkenyl Sulfoxides”. Fernández de la Pradilla, R.; Morente, M.; Paley, R. S. Tetrahedron Lett. 1992, 33, 6101−6102.
S
p-Tol
OSX
R
O
p-TolNaI, AcOH, 5 min X = I, Br, Cl
orR
ZnX2C6H6, rt
“Evidence for “Stable” Organocopper Intermediates in the Reaction between Me2CuLi·LiI and Allylic Sulfinyl Mesylates”. Fernández de la Pradilla, R.; Rubio, M. B.; Marino, J. P.; Viso, A. Tetrahedron Lett. 1992, 33, 4985−4988.
C C Cn-Bu (CH2)2Ph
HH
Cu
n-Bu H
SO
p-Tol
L MeO
S
n-Bu
Ph(CH2)2
MsO
p-Tol
“Strain-Directed Bridge Cleavage of Phenylsulfonyl 7-Oxabicyclo[2.2.1]heptane Derivatives: Application to the Total Synthesis of Carba--DL-glucopyranose”. Aceña, J. L.; Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1992, 57, 1945−1946.
1) PhSCl2) LiAlH4
3) KOH, BnCl4) MMPP
n-BuLi
Tol, TMEDA,CH2Cl2, –78 °C
1) NaHg, MeOH
2) OsO4, Me3NO3) BF3·OEt2, EtSH
Carba--DL-glucopiranose
O
CO2H
OPhSO2
BnO OBnBnO
OHOBn
HO
OHOH
OH
HO
8 steps28% overall yield
PhSO2
“Temperature-Controlled Synthesis of 4,7-Dioxatricyclo[3.2.1.03,6]octane Derivatives”. Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1992, 57, 772−774.
O CH3
OH
O CH3
OHPhSe
ClO CH3
PhSe
O
CH2Cl2, –78 °C, 10 : 90CH3CN, reflux, 95 : 5
n-BuLiO
OH
OPhS
O
O
OH
PhS
PhSeCl
1991 “Highly Diastereoselective bis-Hydroxylation of a Protected Conduritol B: A Short Route to myo-Inositol Derivatives”. Arjona, O.; de Dios, A.; Fernández de la Pradilla, R.; Plumet, J. Tetrahedron Lett. 1991, 32, 7309−7312.
Conduritol B
OsO4, Me3NO HO
OTBSTBSO
BnO
OHOAc
OTBSTBSO
BnO
OAc
MESO FORM91 : 9
7-ONNAcO
OTBSTBSO
BnO
OAcOAc
“Fine-Tuned Remote Control of Electrophilic Additions to Substituted Norbornenes”. Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. J. Org. Chem. 1991, 56, 6227−6229.
R
H
R
HPhSe
Br
R
HBr
PhSe
PhSCl 1 : 15 R = OH1 : 10 R = OH
25 : 1 R = CH2OH
PhSeBr
20
“Asymmetric Carbon-Carbon Bond Formation via Sulfoxide-Directed SN2’ Displacements of Acyclic Allylic Mesylates”. Marino, J. P.; Viso, A.; Fernández de la Pradilla, R.; Fernández, P. J. Org. Chem. 1991, 56, 1349−1351.
MeCuCNMgBr
MeCuCNLi+
6 : 94
6 : 94
+
MsO
Ph
S
O
p-TolEt
MsO
Ph
SO
p-TolEt
S
O
p-TolEt
PhMe
S
O
p-Tol
PhMe
S
O
p-TolEt
PhMe
Et
SO
p-Tol
PhMe
Et
“Novel Highly Regioselective O-Alkylation and O-Acylation of myo-Inositol”. Zapata, A.; Fernández de la Pradilla, R.; Martín-Lomas, M.; Penadés, S. J. Org. Chem. 1991, 56, 444−447.
OH
OHHO
OH
HO OH
OBEt2OBEt2Et2BO
OBEt2
Et2BO OBEt2
OH
OBnHO
OH
HO OH
“Synthesis of 1D-1,2-Anhydro-myo-inositol”. Jaramillo, C.; Fernández de la Pradilla, R.; Martín-Lomas, M. Carbohydr. Res. 1991, 209, 296−298.
O
BnO
OBn
BnO
OH
BnO
OBn
BnO
O
OH
HO
OH
HO
O CONDURITOL B EPOXIDED-Glucose
1990 “Regioselective Electrophilic Additions to 2-Alkoxy- and 2-Alkoxymethyl-7-oxabicyclo[2.2.1]hept-5-ene Derivatives”. Arjona, O.; Fernández de la Pradilla, R.; Pita-Romero, I.; Plumet, J.; Viso, A. Tetrahedron 1990, 46, 8199−8206.
O OBn
H
O OBn
HPhSe
BrO OBn
HBr
PhSe
1 : 5
O H
CH2OBz
O
CH2OBz
CH2OBzO H
CH2OBzPhSe
Br
O
CH2OBzPhSe
Br CH2OBz
PhSeBr
PhSeBr PhSeBr
“Ring Opening SN2’ Reactions of 7-Oxanorbornenes by Organolithium Reagents. Regio- and Stereospecific Synthesis of Substituted Cyclohexenediols”. Arjona, O.; Fernández de la Pradilla, R.; Martín-Domenech, A.; Plumet, J. Tetrahedron 1990, 46, 8187−8198. “Polar vs Steric Effects in the 1,3-Dipolar Cycloaddition Reactions of Acetonitrile Oxide and 2-endo-Acetoxy-5-halo-7-oxabicyclo[2.2.1]hept-5-en-2-exo-carbonitrile”. Arjona, O.; de Dios, A.; Fernández de la Pradilla, R.; Mallo, A.; Plumet, J. Tetrahedron 1990, 46, 8179−8186. “Improved Preparation of Acetals of myo-Inositol and its (±)-1-O-Benzyl Ether: Conformational Analysis of di-O-Isopropylidene-myo-inositol Derivatives”. Fernández de la Pradilla, R.; Jaramillo, C.; Jiménez-Barbero, J.; Martín-Lomas, M.; Penadés, S.; Zapata, A. Carbohydr. Res. 1990, 207, 249−257. “Regio- and Stereocontrolled Synthesis of Hydroxycyclohexenyl Sulfones from Oxanorbornenes”. Arjona, O.; Fernández de la Pradilla, R.; Mallo, A.; Plumet, J.; Viso, A. Tetrahedron Lett. 1990, 31, 1475−1478.
O CH3
OBnPhSO2
O CH3
OBn
PhSO2
CH3
OBnPhSO2
CH3
OBn
PhSO2OH
R1
R1
OH
R1Li
Tol
R1Li
Tol
21
1989 “Regio- and Stereospecific Synthesis of Substituted Cyclohexenediols from 7-Oxabicyclo[2.2.1]hept-5-en-2-ols and Organolithium Reagents”. Arjona, O.; Fernández de la Pradilla, R.; García, E.; Martín-Domenech, A.; Plumet, J. Tetrahedron Lett. 1989, 30, 6437−6440.
O
R
OH O
OH
R
R
R1
OH
OH
OH
R1
OH
RR1Li R1Li
“1,3-Dipolar Cycloadditions between Nitrile Oxides and Substituted 7-Oxabicyclo[2.2.1]heptenes”. Arjona, O.; Domínguez, C.; Fernández de la Pradilla, R.; Mallo, A.; Manzano, C.; Plumet, J. J. Org. Chem. 1989, 54, 5883−5887.
O CN
OAc
ClO CN
OAcPhSO2
O CN
OAc
ON
Ar
Cl
H
O CN
OAc
NO
H
SO2Ph
Ar
“Bromination Reactions of 2-Substituted Derivatives of 7-Oxabicyclo[2.2.1]hept-5-ene”. Arjona, O.; Fernández de la Pradilla, R.; García, L.; Mallo, A.; Plumet, J. J. Chem. Soc. Perkin Trans. II 1989, 1315−1318. “Regioselective Electrophilic Additions to 2-Oxygenated-7-oxabicyclo[2.2.1]hept-5-enes: A Simple Entry into the 4,7-Dioxatricyclo[3.2.1.03,6]octane Skeleton”. Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Viso, A. Tetrahedron 1989, 45, 4565−4578.
PhSClO OH
Me
O OH
MeE
XO Me
OH
O Me
OHPhSe
ClO Me
O
PhS
EX = PhSeCl, PhSCl
EX PhSeCl
“Stereoselectivity of Organometallic Reagents Addition to 7-Oxabicyclo[2.2.1]hept-5-en-2-one”. Arjona, O.; Fernández de la Pradilla, R.; Mallo, A.; Pérez, S.; Plumet, J. J. Org. Chem. 1989, 45, 4158−4164.
R2CuLiO R
OH
O O OH
R
RLi
óRMgX O
Alcohol endo Alcohol exo
1988 “New Functionalizations of Oxanorbornenic Systems via 1,3-Dipolar Cycloadditions with C,N-Diphenylnitrone”. Arjona, O.; Fernández de la Pradilla, R.; Pérez, R. A.; Plumet, J. Tetrahedron 1988, 44, 7199−7204.
O CN
OAc
O CN
OAc
NO
Ph
Ph
H
H
O CN
OAc
ONPh
H
HPh
NPh
Ph
O
“Chemo- and Stereoselective Functionalization of 7-Oxabicyclo[2.2.1]hept-5-en-2-one Derivatives with the System Trichloroacetyl Chloride/Zn(Cu)”. Arjona, O.; Fernández de la Pradilla, R.; Pérez, S.; Plumet, J. Tetrahedron 1988, 44, 1235−1240.
Cl2CCOO
O
O
OO
ClCl O
OH
OH O
OO
ClCl O
OO
ClCl
O
O
“Reduction of N-Substituted 1-Acetyl- and 1-Benzoyl-ethaneimines”. Alcaide, B.;Arjona, O.; Fernández de la Pradilla, R.; Plumet, J.; Rodríguez-Campos, I. M.; Santesmases, M. J. J. Chem. Research, (S) 1988, 98−99; (M), 1988, 932.
22
1987 “Sulfoxide-Directed Lactonization: Asymmetric Synthesis of Porosin Intermediates”. Marino, J. P.; Fernández de la Pradilla, R.; Laborde, E. Synthesis 1987, 1088−1091.
Ra-Ni
POROSIN
Cl2CCOMe
Ar1 Br
MeO
MeO
Me
Ar1 SO
p-TolO O
Me
Ar1
p-TolS O O
Me
Ar1
O O
Me
Ar1
CO2Me
O
O
Me
O
OCH3CH3O
CH3O
= Ar1
“Regio- and Stereoselective Electrophilic Additions to exo and endo-2-Hydroxy-2-methyl-7-oxabicyclo [2.2.1]hept-5-ene”. Arjona, O.; Fernández de la Pradilla, R.; Pérez, R. A.; Plumet, J.; Viso, A. Tetrahedron Lett. 1987, 28, 5549−5550. “Stereoselectivity of the Reaction between 7-Oxabicyclo[2.2.1]hept-5-en-2-one and Organocuprate Reagents”. Arjona, O.; Fernández de la Pradilla, R.; Manzano, C.; Pérez, S.; Plumet, J. Tetrahedron Lett. 1987, 28, 5547−5548. “Regio- and Stereoselectivity of the Reaction between Cyanocuprates and Cyclopentene Epoxides. Application to the Total Synthesis of Prostaglandins”. Marino, J. P.; Fernández de la Pradilla, R.; Laborde, E. J. Org. Chem. 1987, 52, 4898−4913.
R
OTES
O R
OTES
MOMOR
MOMO
TESOH
CO2Et
RMOMO
O
O
1) LiAlH4
2) MOMClPGF2
1) Et3NHF
2) PBPH
N2CHCO2Et
O
HO
(CH2)6CO2H
C5H11
OH
HO
HO
(CH2)6CO2H
C5H11
OH
HO
HO
C5H11
OH
(CH2)3CO2H
PGE1PGF1
PGF2
1986-1981 “Chemo- and Stereoselective Functionalization of 7-Oxabicyclo[2.2.1]hept-5-en-2-one with Dichloroketene”. Arjona, O.; Fernández de la Pradilla, R.; Pérez, S.; Plumet, J.; Carrupt, P.-A.; Vogel, P. Tetrahedron Lett. 1986, 27, 5505−5506. “Stereospecific Synthesis of -Butyrolactones from Acyclic Vinyl Sulfoxides: an Asymmetric Synthesis of Optically Pure Oak Lactones”. Marino, J. P.; Fernández de la Pradilla, R. Tetrahedron Lett. 1985, 26, 5381−5384.
Cl3CCOCl
Zn(Cu)Me
n-Bu S
p-Tol
OO
O
ClClMe
n-Bu
p-TolSO
O
Me
n-Bu OO
Me
n-Bu
¨
Bu3SnH
AIBN
OAK LACTONES
R
S
¨ Op-Tol
C
S
R
O
O-
p-Tol S
R
O-O O
O
Cl
Cl
R
p-TolS+
:
OCCl
Cl p-Tol
¨
23
“Stereocontrolled Synthesis of Prostaglandins from Cyclopentadiene Monoepoxide”. Marino, J. P.; Fernández de la Pradilla, R.; Laborde, E. J. Org. Chem. 1984, 49, 5279−5280.
RCuCNLi
KF
OHO
R R
O
O R
TESO
O R
TESO
HO
R1
R
TESO
HO
R1
R
O
HO
R1
1) t-BuOOH,
VO(acac)2
2) CrO3.Pyr
1) LDA
2) Et3SiCl
R1CuCNLi (LiI)
R1CuCNLi
“Stereochemistry of Imino Group Reduction. 2. Synthesis and Assignment of Configuration of Some N-(1-Phenylethyl)-1,2-diaryl-2-aminoethanols”. Alcaide, B.; Fernández de la Pradilla, R.; López-Mardomingo, C.; Pérez-Ossorio, R.; Plumet, J. J. Org. Chem. 1981, 46, 3234−3238.
Ar C CO
N CHAr
CH3
PhAr C
HC
OH HN
HC
Ar
CH3
Ph
Ar C CO H
NHC
Ar
CH3
PhH2, Pd(C)
LiAlH4
LiAlH4
Recommended