Reviews and Full Papers in Chemical Synthesis

January 19, 2021 • Vol. 53, 193–390

2Synthesis of Peripherally Arylated Tetrathiafulvalenes Extended with an Anthraquinoid Spacer via Pd-Catalyzed C–H Arylation and Construction of a Double-Helical Cobalt-Based Metal-Organic Framework

A. Yoshimura, K. Henmi, H. Kimura, R. Sakakibara, R. Ochi, T. Shirahata, H. Yorimitsu, Y. Misaki

Special TopicFunctional Organic MoleculesEditor: Franziska Schoenebeck

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Reviews and Full Papers in Chemical Synthesis

2021Vol. 53, No. 2

January IISynthesis

Synthesis

Cover Design: © Thieme

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Synthesis 2021, 53, 193–214DOI: 10.1055/s-0040-1705939

S. PonraB. BoudetP. Phansavath*V. Ratovelomanana-Vidal*Chimie ParisTech-CNRS, France

Synthesis

as

Recent Developments in Transition-Metal-Catalyzed Asymmetric Hydrogenation of Enamides

H2

Rh

IrRu

Ni Co

OH

NHAcR

CO2Me

NHAc

ArCHO

NHAc

NHAc

PR22

R1

O

NHAc

R2

R1

CNAcHN

R

NH

O

OR

N

HN R

O

Ph

*

AcHN

Ar

O

OR

OR

NBn

O

CO2H( )n

CF3

NHAcR

CO2Me

NHAc

R2

R1

R3

NPh

R

O

SO2R2NHAc

R1

NO2

NHAc

R

NHAc

R

NHAc

OMOM

R1

R2F

CO2R'

NHAc

R

Ar

HN

O

*R NHAc

R

*

© 2021. Thieme. All rights reserved.

Review

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Synthesis 2021, 53, 215–237DOI: 10.1055/s-0040-1707298

L. Carceller-FerrerG. BlayJ. R. Pedro*C. Vila*Universitat de València, Spain

Recent Advances in Catalytic Enantioselective Synthesis of Pyrazolones with a Tetrasubstituted Stereogenic Center at the 4-Position

AsymmetricNucleophilic

pathway

NN

PhO

Y

Me

NN

R1

O

X

R2

Y

AsymmetricElectrophilic

pathway

NN

PhO

Y

Me

N

N

PhO

Me

R

AsymmetricElectrophilic-Nucleophilic

pathway

Review

215

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Synthesis 2021, 53, 238–254DOI: 10.1055/s-0040-1707268

F. ZhangL. XinY. YuS. Liao*X. Huang*Fujian Province University, P. R. of ChinaFujian Institute of Research on the Structure of Matter, P. R. of China

Synthesis

Synthesis

is s

t

Recent Advances in Palladium-Catalyzed Bridging C–H Activation by Using Alkenes, Alkynes or Diazo Compounds as Bridging Reagents

nArPdn

thermodynamicallystable palladacycle

Ar

C–H bondactivation

H

Pd

nAr

n = 0, 1

alkene

alkyne

diazocompound

H

nAr

R1

Pd

R2

H

nAr

R1

Pd

R2

ArPd

R1 R2

O

H

S

© 2021. Thieme. All rights reserved.

hort Review

238

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Synthesis 2021, 53, 255–266DOI: 10.1055/s-0040-1707270

T. EdlováM. ČubiňákT. Tobrman*University of Chemistry and Technology, Prague, Czech Republic

as

Cross-Coupling Reactions of Double or Triple Electrophilic Templates for Alkene Synthesis

(R)X

X(R)

OFG

X(R) R

RR

R

R B(OH)2

RBu3Sn

R MgX

R ZnX+

X = F, Cl, Br

chemo- and stereoselectivetransformations

OFG = OTs, OTf, OC(O)R, OP(O)(OR)2

TM-cat

S

hort Review

255

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Synthesis 2021, 53, 267–278DOI: 10.1055/s-0040-1707269

C. BandariK. M. Nicholas*University of Oklahoma, USA

Deoxygenative Transition-Metal-Promoted Reductive Coupling and Cross-Coupling of Alcohols and Epoxides

R R

R1

R1R

Ar R

O

R R1

R1 OHAr X

R1 M

R OH

R

R

R

OH

R1

R1

OH

R

R3R2

R2

R3

R1

OH

R

O

R2 R2

RR1

R

OHR2

R R1

R R1

R1

R2

S

hort Review

267

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Synthesis 2021, 53, 279–295DOI: 10.1055/s-0040-1706535

Á. MagyarK. JuhászZ. Hell*Budapest University of Technol-ogy and Economics, Hungary

Synthesis

Synthesis

is s

t

The Application of 4Å Molecular Sieves in Organic Chemical Syntheses: An Overview

4A Molecular Sieves

Additive

Catalyst Co-catalystSupport

S

© 2021. Thieme. All rights reserved.

hort Review

279

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Synthesis 2021, 53, 296–308DOI: 10.1055/s-0040-1707318

M. M. HorninkA. U. LopesL. H. Andrade*University of São Paulo, Brazil

as

Biobased Spiroimides from Itaconic Acid and Formamides: Molecular Targets for a Novel Synthetic Application of Renewable Chemicals

Feature

296

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Synthesis 2021, 53, 309–317DOI: 10.1055/s-0040-1707313

M. SakturaS. FrankowskiB. JoachimŁ. Albrecht*Lodz University of Technology, Poland

Aminocatalytic Synthesis of Uracil Derivatives Bearing a Bicyclo[2.2.2]octane Scaffold via a Doubly Cycloadditive Reaction Cascade

N

N

O

O

OO

R

N

NO

OCHO

R

OHCR

aminocatalyticdoubly cycloadditive

reaction cascade

NH Ph

Ph

10 examples45–86% yield

>25:1 drfrom 97:3 to >99:1 er

R = Ph, 4-BrC6H4, 4-ClC6H4, 4-O2NC6H4,4-MeC6H4, 3-MeC6H4, 2-MeC6H4, 4-MeOC6H4,

2-MeOC6H4, 2-furyl

+

Feature

309

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Synthesis 2021, 53, 318–325DOI: 10.1055/s-0040-1707896

A. Arjona-EstebanA. RauschM. O. VysotskyF. Würthner*Universität Würzburg, Germany

Synthesis

Synthesis

is s

t

Merocyanine Dyes with Extended Polymethine Chains by Simple Two-Step Condensation Sequence

O

O

O

O

MeNHOH80 °C, 20 h

pressure flask

O

ON

Bu

2-hexanone

O

N

Bu

KOAc, Ac2Or.t., 1 h

S

© 2021. Thieme. All rights reserved.

pecial Topic

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Synthesis 2021, 53, 326–331DOI: 10.1055/s-0040-1707177

A. YoshimuraK. HenmiH. KimuraR. SakakibaraR. OchiT. ShirahataH. YorimitsuY. Misaki*Ehime University, Japan

as

Synthesis of Peripherally Arylated Tetrathiafulvalenes Extended with an Anthraquinoid Spacer via Pd-Catalyzed C–H Arylation and Con-struction of a Double-Helical Cobalt-Based Metal-Organic Framework

S

pecial Topic

326

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Synthesis 2021, 53, 332–337DOI: 10.1055/s-0040-1707288

F. J. WidnerC. KieningerK. WurstE. DeeryA. D. LawrenceM. J. WarrenB. Kräutler*University of Innsbruck, Austria

Synthesis, Spectral Characterization and Crystal Structure of Chlororhodibalamin: A Synthesis Platform for Rhodium Analogues of Vitamin B12 and for Rh-Based Antivitamins B12

N

N

Cl

O

+ RhIII

N

N

R

O

+ RhIII

N

N

O

+HH

S

pecial Topic

332

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Synthesis 2021, 53, 338–343DOI: 10.1055/s-0040-1707290

F.-Z. YanY.-G. ShaoZ. ZhangY.-F. ShenX.-C. HuangP.-L. ZhangS. Li*Hangzhou Normal University, P. R. of China

Synthesis

Synthesis

is s

t

Synthesis of Catenanes from a BMP32C10-Based Cryptand Tuned by the Linkage Length of Paraquat Salts

S

© 2021. Thieme. All rights reserved.

pecial Topic

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Synthesis 2021, 53, 344–347DOI: 10.1055/s-0040-1705950

P. MeiR. KurosakiA. MatsumotoH. Yamada*N. Aratani*Nara Institute of Science and Technology (NAIST), Japan

as

One-Pot Synthesis of a Cyclic Pyrene Octamer from Two Bifunctional-ized Pyrene Monomers

tBu

pinB Bpin

tBu

I I

tBu

tBu

tBu

tBu

tBu

tBu

tBu

tBu+

Cs2CO3toluene/DMF

Pd NH2Cl

PtBu3

One-pot cyclization!

2.8%

S

pecial Topic

344

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Synthesis 2021, 53, 348–358DOI: 10.1055/s-0040-1707278

J. O. StrelnikovaN. V. RostovskiiO. V. KhoroshilovaA. F. KhlebnikovM. S. Novikov*St. Petersburg State University, Russian Federation

An Efficient Synthesis of Functionalized 2H-1,3,5-Oxadiazines via Metal-Carbenoid-Induced 1,2,4-Oxadiazole Ring Cleavage

R2RO2C

MLn

R2RO2C

N2

MLn

O

NN

Ar/Alk

R1R2

CO2R

• 24 examples• yield up to 97%

N

OAr

RO2C

R2

N

O

N

Ar/Alk

M = Rh, Cu

R1 = H R1 ≠ H

R1

H, CN, CF3, CO2Me

H, Ar, Alk, OMe, NMe2

N4-attack N2-attack

Paper

348

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Synthesis 2021, 53, 359–364DOI: 10.1055/s-0040-1706551

V. LösleO. KataevaH.-J. Knölker*Technische Universität Dresden, Germany

Synthesis

Synthesis

is s

t

First Total Synthesis and Investigation of the X-ray Crystal Structure of the Pyrano[3,2-a]carbazole Alkaloid Clausenalansine A

N

H

O

CHOHO

N

H

O

HOTBDPSO

Br OMeH2N O

H+ +

koenine clausenalansine A

© 2021. Thieme. All rights reserved.

Paper

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Synthesis 2021, 53, 365–370DOI: 10.1055/s-0040-1706422

I. CasadiaT. O. DaherS. MouraD. F. BackE. FaoroC. S. SchwalmG. A. CasagrandeG. C. PaveglioL. Pizzuti*Universidade Federal da Grande Dourados, Brazil

as

A Domino Reaction for the Synthesis of Novel 1,3-Dihydrofuro-[3,4-c]pyridines from Pyridoxal and Ketones

NOH

OO

Ar

NOH

O

OH

HCl·

O

Ar+

dominoClaisen–Schmidt condensation–

oxa-Michael addition

Representative examples:

NOH

OO

NOH

OO

NOH

OO

NOH

OO

S

65% 90% 67%53%

9 compounds53–90%

room temperaturehazardless solvent

easy workupno chromatographic purification

Paper

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Synthesis 2021, 53, 371–382DOI: 10.1055/s-0040-1705941

V. A. TkachukV. O. ShishkanuT. M. TkachukS. V. ShishkinaO. V. Hordiyenko*Taras Shevchenko National Uni-versity of Kyiv, Ukraine

2-Carbamimidoylbenzoic Acid as a New Effective and Available Precur-sor for the Synthesis of Substituted 2-(Pyrimidin-2-yl)-benzoic Acids

CO2HNH2

NH

HN

N

CO2H

R1

O

OMe

O

Ar1

O

MeO

HO

Ar1

N

N

69%

Ar1 = 4-ClC6H4

CO2H

O R2 (H, CF3)MeO

O

OAr2

OMe

ON

N

R2CO2H

– Ar2OH (Ar2 = 4-ClC6H4, 2-O2NC6H4)

1,3-dielectrophile

73–82%

R1 = Me, Et, Ph, OH, NH2 (71–92%)

N

N

R1

O

O

H2O (R1 = NH2)

– H2O

R1 = Me, Et, Ph, NH2 (72–95%)

/

Paper

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Synthesis 2021, 53, 383–390DOI: 10.1055/s-0040-1707356

X. YeJ. HuangZ. DengJ. YuanY. Peng*Jiangxi Normal University, P. R. of China

Synthesis

Synthesis

is s

t

Palladium-Catalyzed Cross-Coupling Reactions of 4-Tosyloxyquinazolines with Indoles: An Efficient Approach to 4-(1H-Indol-1-yl)quinazolines

N

N

R1

OTs

X +

N

N

R1

X

NSPhos (10 mol%)

toluene, 110 °C

Pd(TFA)2 (5 mol%)

K2CO3 (2 equiv)NH

Y

Y

26 examples

© 2021. Thieme. All rights reserved.

Paper

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