1

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.

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“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.

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“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