Imprimatur:

Date, Signaturetoc0620.fm 3/13/20

Accounts andRapid Communications in Chemical Synthesis

2019Vol. 31, No. 6

April ISyn lett

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Synlett 2019, 30, 521–522DOI: 10.1055/s-0040-1708008

A. J. Burke*University of Évora, Portugal

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Cluster Preface: ISySyCat2019

Cluster

521

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Synlett 2020, 31, 523–534DOI: 10.1055/s-0039-1690722

Y. Sohtome*M. Sodeoka*RIKEN Cluster for Pioneering Re-search, Japan

Multiselective Catalytic Asymmetric Reactions Using -Keto Esters as Pronucleophiles

Electrophiles

R1

CO2R2

O

E

NR4 O

R3

O

CO2R2

R1

ON

OH

CO2R2

R1

R3

R4

Spontaneouscyclization

Nitrones or

nitrile oxides Three chiral centers or

Two chiral centers with N=C bond

R1

CO2R2

OH

E

Two chiral centers

Chemo-, regio-, diastereo-, and enantioselective

Reduction

Chemo- and enantioselective DiastereoselectiveR1

CO2R2

OChiral transition-

metal catalyst

Account

523

VI

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Synlett 2020, 31, 535–546DOI: 10.1055/s-0039-1690777

S. Rossi*T. BenincoriL. M. RaimondiM. Benaglia*Università degli Studi di Milano, Italy

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3,3′-Bithiophene-Based Chiral Bisphosphine Oxides as Organocatalysts in Silicon-Derived Lewis Acid Mediated Reactions

Account

535

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Synlett 2020, 31, 547–552DOI: 10.1055/s-0039-1690797

V. ElumalaiJ. H. Hansen*UiT The Arctic University of Nor-way, Norway

as

A Green, Scalable, One-Minute Synthesis of Benzimidazoles

Cluster

547

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Synlett 2020, 31, 553–558DOI: 10.1055/s-0039-1691533

C. AlvesC. GrossoP. BarrulasJ. A. PaixãoA. L. CardosoA. J. BurkeA. LemosT. M. V. D. Pinho e Melo*University of Coimbra, Portugal

Asymmetric Neber Reaction in the Synthesis of Chiral 2-(Tetrazol-5-yl)-2H-Azirines

Cluster

553

VII

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Synlett 2020, 31, 559–564DOI: 10.1055/s-0039-1691523

P. MasséS. Choppin*L. Chiummiento*G. HanquetF. ColobertUniversité de Strasbourg / Uni-versité de Haute- Alsace, ECPM, FranceUniversity of Basilicata, Italy

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Unintended Formation of a 26-Membered Cycle in the Course of a Novel Approach to Myricanol, a Strained [7,0]-Metacyclophane

OBn

MeO

MeO

BnO

O

OH

MeO

MeO

HOHO

(±)-myricanol

13Ru

OBn

MeO

MeO

BnO

OBn

OMe

OMe

OBn

Unintended RCM

Ru O

O

( )2

( )2

( )2

( )2

26

DesiredRCM

Cluster

559

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Synlett 2020, 31, 565–574DOI: 10.1055/s-0037-1610744

S. A. TrofymchukD. V. KliukovskyiS. V. SemenovA. R. KhairulinV. O. ShevchenkoM. Y. BugeraK. V. TarasenkoD. M. Volochnyuk*S. V. Ryabukhin*Enamine Ltd., UkraineNational Academy of Sciences of Ukraine, UkraineTaras Shevchenko National Uni-versity of Kyiv, Ukraine

as

Semi-Industrial Fluorination of -Keto Esters with SF4: Safety vs Efficacy

R3 R2

O

OEt

OR4

R3 R2OH

O

R4

F F25 examples

> 50 g from 1 run

R1R1

R = H or alkyl

S A F E T Y

vsE F F I C A C Y

5+ step routes, DAST on a deoxofluorination step

two-step routeSF4, HF

Cluster

565

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Synlett 2020, 31, 575–580DOI: 10.1055/s-0039-1691570

Y. ZiM. LangeP. SchülerS. KrieckM. WesterhausenI. Vilotijevic*Friedrich Schiller University Jena, Germany

Synthesis of -Lactams via Enantioselective Allylation of Anilines with Morita–Baylis–Hillman Carbonates

Ar1

OBoc

CO2Me

(DHQD)2AQN (10 mol%)

Ar2

NH2 Ar1 CO2Me

NHAr2

Ar1

NOAr2

1. Sn(HMDS)2

up to 97% yieldup to 98:2 er

single isomerup to 93% yield

good control of diastereoselectivity

C6H12, rt 2. H2, Pd/C

Cluster

575

VIII

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Synlett 2020, 31, 581–586DOI: 10.1055/s-0037-1610751

MD T. RahmanS. WharryM. Smyth*H. Manyar*T. S. MoodyAlmac Sciences Ltd., UKQueen’s University Belfast, UK

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FAST Hydrogenations as a Continuous Platform for Green Aromatic Nitroreductions

Flo

w0.

5–5.

0 m

L/m

in

5% Pd-CPacked-bed

6–21 cm80 °C

H2

(5–10 bar)

COOH

NO2

PNBA

COOH

NH2

PABA

ExcessH2

BPR

MFC

G/L

MFC = mass flow controllerG/L = gas-liquid separatorBPR = back-pressure

Cluster

581

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Synlett 2020, 31, 587–591DOI: 10.1055/s-0039-1690851

B. Qu*L. P. SamankumaraA. SahaM. G. SchumerZ. S. HanN. HaddadC. A. BusaccaN. K. YeeM. C. KozlowskiJ. J. SongC. H. SenanayakeBoehringer Ingelheim Pharma-ceuticals, Inc., USA

as

Rational Design of New Dihydrobenzooxophosphole-Based Lewis Base Organocatalysts

Ph

O

Ar Ph

O

Ar

NH HNO O

OP P

O

OMe MeO

O O

tBu tBu

up to 90.2:9.8 er 94% yield

HSiCl3 (5 equiv), acetonitrile, 0 °C

(10 mol%)

Strong H-bonds enhance reactivity of the new catalyst

Cluster

587

Thi

s do

cum

ent w

Synlett 2020, 31, 592–594DOI: 10.1055/s-0039-1689925

G. Di MauroM. DrescherS. TkaczykN. Maulide*University of Vienna, Austria

Aminoxylation of Thioalkynes through Radical-Polar Crossover

S

S

O

ON

N

O

TfOH

radical-polar crossover aminoxylation reaction

9 examplesup to 65% yield

radical-polar crossover

Cluster

592

IX

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Synlett 2020, 31, 595–599DOI: 10.1055/s-0039-1690160

D. Xu*L. FrankT. NguyenA. StumpfD. RussellR. AngelaudF. GosselinGenentech Inc., USA

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Magnesium-Catalyzed N2-Regioselective Alkylation of 3-Substituted Pyrazoles

R1

NHN

R2

R1

NN

R2

OR3

R1

NN

R2

R3O

+

cat. Mg2+, baseyield up to 90%

baseyield up to 70%

N2/N1 up to 98:213 examples

N1/N2 up to 99:115 examples

R3

O

Br2 1

2 1

2 1

Cluster

595

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Synlett 2020, 31, 600–604DOI: 10.1055/s-0039-1690990

M. M. SalgadoA. ManchadoC. T. NietoD. DíezN. M. Garrido*Universidad de Salamanca, Spain

as

Asymmetric Synthesis of 2,3,6-Trisubstituted Piperidines via Baylis–Hillman Adducts and Lithium Amide through Domino Reaction

4-BnOC6H4COOMe

OAc4-BnOC6H4

COOMe

N

COOH

Ph

Ph

NH

4-HOC6H4

MeOOC

4-FC6H4

Ph NLi

Ph

(R)-1 4-FC6H4MgBr

yield: 69%chiral lithium domino

reaction to d-amino acids three points of variation

on chiral 2,3,6-trisubstituted piperidines

overall yield: 20%

Cluster

600

Thi

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Synlett 2020, 31, 605–609DOI: 10.1055/s-0039-1690736

F. SebestS. HaselgroveA. J. P. WhiteS. Díez-González*Imperial College London, UK

Metal-Free 1,2,3-Triazole Synthesis in Deep Eutectic Solvents

Cluster

605

X

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Synlett 2020, 31, 610–614DOI: 10.1055/s-0039-1691524

A. RouxF. Cisnetti*Université Clermont Auvergne, France

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Click Variations on the Synthesis of 2-Nitrophenyl-4-aryl-1,2,3-triazoles without Isolation of 2-Nitrophenyl Azides

F

NO2

N

NO2

NN

X

X

N3

NO2X

NaN3

Onot isolated

N

NO2

NN

X

EWG

EWG

I

SiMe3

Pd cat.Cu cat.

+

DBU cat.

H

Cluster

610

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Synlett 2020, 31, 615–621DOI: 10.1055/s-0039-1690781

E. P. Carreiro*A. M. SenaA. PuertaJ. M. PadrónA. J. BurkeUniversity of Évora, Portugal

as

Synthesis of Novel 1,2,3-Triazole-Dihydropyrimidinone Hybrids Using Multicomponent 1,3-Dipolar Cycloaddition (Click)–Biginelli Reactions: Anticancer Activity

N3

O

O

O

H2N NH2

multicomponentclick–Biginelli reactionsin one pot

NH

NH

O

NNN

Ph

X

Y

NH

NH

O

NNN

Ph

X

Y

NNN

R

hybrids A

X

Y

hybrids B

R

Br

NO

O

multistep sequence:brominationazidationCuAAC

MW MW

X

Y

= H, Cl, OBn

= H, Br, OMe

5 examplesup to 57% yield

16 examplesup to 99% yield

Cu(I)

antiproliferative assay against the cancer cell lines: A549, SW1573, HBL-100, T-47D, HeLa, WiDr

Cluster

615

Thi

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Synlett 2020, 31, 622–626DOI: 10.1055/s-0039-1691497

A. Capretz-AgyF. S. Fernandes*M. T. Rodrigues Jr. C. ContiF. Coelho*University of Campinas, Brazil

Aza-Morita–Baylis–Hillman Reaction with Vinyl-oxadiazoles: An Expe-ditious Approach to Access New Heterocyclic Arrangements

O N

N AcOH (1.05 equiv)toluene (1 M), r.t.

R3

R1

R1 and R2 = EDG and/or EWG R3 = Ph, 4-O2NC6H4, 4-MeOC6H4, CHPh2

• New aza-MBH adducts• Highly atom economy• Potential biological activity• 16 Examples, 31–93% yield• 30 min to 24 h

H

NSO2R2

NN

(1.05 equiv)

vinyl-oxadiazoles

NH

N

NOR3

SR2

O

O

R1

Cluster

622

XI

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Synlett 2020, 31, 627–631DOI: 10.1055/s-0037-1610746

R. D. ReevesC. N. KinkemaE. M. LandwehrL. E. VineJ. M. Schomaker*University of Wisconsin, USA

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Stereodivergent Metal-Catalyzed Allene Cycloisomerizations

R1 •

R2

R3

ab

gE

OO

R4

ER2

R3

R1O

R4

ER2

R3

R1

R4

cat. LnPd

syn-selectiveanti-selective

a

g cat. LAuCl

Cu(OTf)2toluene

NaOMeTHF

substrate-controlled stereodivergence based on differing mechanisms

Cluster

627

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Synlett 2020, 31, 632–634DOI: 10.1055/s-0039-1690828

J. R. M. FerreiraR. Nunes da SilvaJ. RochaA. M. S. SilvaS. Guieu*University of Aveiro, Portugal

as

1,2,4-Triphenylpyrroles: Synthesis, Structure and Luminescence Prop-erties

NH2

R3

N

R1

R3

R2

O

R1 R2

Me

NO2

5 examplesup to 34% yield over 3 stepsR1, R2, R3 = H, OMe, NMe2

Et2NH, DBU

O

R1 R2

NO2 i) KOHii) H2SO4

Cluster

632

Thi

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