Imprimatur:

Date, Signaturetc2319ss.fm 11/7/19

Reviews and Full Papers in Chemical Synthesis

2019Vol. 51, No. 23

December ISyn thesis

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Synthesis 2019, 51, 4311–4337DOI: 10.1055/s-0037-1611914

F. DénèsJ. FarardJ. Lebreton*Université de Nantes, France

Syn thesis

as

Synthesis of 13C-Labeled Steroids

2,3,4-13C3-1,4-androstadien-3,17-dione

17.8 min

284.1674

*

**

Me

Me O

O

H

H HHPLC

287.1764

MS

Review

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Synthesis 2019, 51, 4338–4347DOI: 10.1055/s-0039-1690679

O. A. Rakitin*N. D. Zelinsky Institute of Organ-ic Chemistry, Russian Federation

Recent Developments in the Synthesis of 1,2,5-Thiadiazoles and 2,1,3-Benzothiadiazoles

NS

NN

SN

R R

NNO

RRR

H2N

R

NO2 NSe

N

RR

R

H2N

R

NH2

HON

RR

NOH

HN

RR

NH

CH2

HON

RR

NS

S

RR

Cl

NS

N

RRR R

R

H2N

R

NO

NS

NSiMe3

R

R

S2Cl2

SOCl2

S4N4

NH4OH

S2Cl2S2Cl2 S2Cl2

S2Cl2

SOCl2

S

hort Review

4338

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Synthesis 2019, 51, 4348–4358DOI: 10.1055/s-0037-1610732

F. LiF. HeR. M. Koenigs*RWTH Aachen University, Germany

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Catalyst-Free [2,3]-Sigmatropic Rearrangement Reactions of Photochemically Generated Ammonium Ylides

NAr EWG

N2visible light(470 nm)

+Ar'

NAr'

Ar EWG

donor–acceptor diazoalkanes

metal-free photochemical rearrangement reactions of ammonium ylides

key features

mild reaction conditionsmetal-free

operationally simplebroad applicability

compatibility withcyclic amines

anilines up to 97% yield33 examples

Feature

4348

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Synthesis 2019, 51, 4359–4365DOI: 10.1055/s-0039-1690694

B. ZilateC. FischerL. SchneiderC. Sparr*University of Basel, Switzerland

as

Scalable Synthesis of Acridinium Catalysts for Photoredox Deuterations

N+Me

R2

Br–

R1 R1NMeBr

R1

R2

OMeOBr

R1

NMeM

R1

M

R1

Mg

THF, 60 °C

N

N

Cl

56

1' 3'

N

N+

Cl

Cl–

Photocatalyst (2.5 mol%)i-Pr3SiSH (30 mol%)

Li2CO3, D2O, NMP, 24 h40 W blue LED

N+Me

R2

Br–

R1 R1

H

M = Mg

PSP

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Synthesis 2019, 51, 4366–4367DOI: 10.1055/s-0039-1689994

Special Topic Cover Page: Halogenation Methods (with a View towards Radioimaging Applications)

S

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4366

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Synthesis 2019, 51, 4368–4373DOI: 10.1055/s-0037-1611885

A. Sutherland*University of Glasgow, UK

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Radiohalogenation of Organic Compounds: Practical Considerations and Challenges for Molecular Imaging

*IR R

18F

or 18F

O

OH

HOHO OH

N CO2Me

NH

NH2

NH

N

N

N

O

CO2EtHO

HO

CO2H

NH2

F 3

R X18F *I

18F 18F

131I

18F

123I

S

pecial Topic

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Synthesis 2019, 51, 4374–4384DOI: 10.1055/s-0039-1690522

S. Milicevic Sephton*X. ZhouS. ThompsonF. I. AigbirhioUniversity of Cambridge, UK

as

Preparation of the Serotonin Transporter PET Radiotracer 2-({2-[(Dimethylamino)methyl]phenyl}thio)-5-[18F]fluoroaniline (4-[18F]ADAM): Probing Synthetic and Radiosynthetic Methods

S

NHBoc

B

NMe2

O

O

18F–, Cu(OTf)2(py)4S

NH2

18F

NMe2

4-[18F]ADAM

4-[18F]2

29%

S

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Synthesis 2019, 51, 4385–4392DOI: 10.1055/s-0039-1690009

K. KitaharaH. MizutaniS. IwasaK. Shibatomi*Toyohashi University of Technol-ogy, Japan

Asymmetric Synthesis of -Chloro--halo Ketones by Decarboxylative Chlorination of -Halo--ketocarboxylic Acids

CO2HR1

O

R2 F

ClR1

O

R2 F

*– CO2

C1

NH2

CO2Et

tBu

tBu

tBu

tBu

up to 90% ee9 examples

77–98% yield

NCSC1 (cat.)

S

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Synthesis 2019, 51, 4393–4400DOI: 10.1055/s-0037-1611884

E. DubostV. BabinF. BenoistA. HébertG. PigréeJ.-P. BouillonF. FabisT. Cailly*Normandie Univ, FranceCHU Côte de Nacre, France

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Improvements of C–H Radio-Iodination of N-Acylsulfonamides toward Implementation in Clinics

NHTs

O

NHTs

O

125IH

1) Pd(OAc)2 (cat.)PTSA (cat.)

0.25 h

2) [125I]NIS, 0.25 hR R

Short reaction time Catalytic No side-products

11 compounds RCC = 27–84%

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Synthesis 2019, 51, 4401–4407DOI: 10.1055/s-0039-1690012

S. ThompsonS. J. LeeI. M. JacksonN. IchiishiA. F. BrooksM. S. Sanford*P. J. H. Scott*University of Michigan Medical School, USAUniversity of Michigan, USA

as

Synthesis of [18F]--Fluoro-,-unsaturated Esters and Ketones via Vinylogous 18F-Fluorination of -Diazoacetates with [18F]AgF

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Synthesis 2019, 51, 4408–4416DOI: 10.1055/s-0037-1611886

J. C. SarieJ. NeufeldC. G. DaniliucR. Gilmour*Westfälische Wilhelms-Universi-tät Münster, Germany

Willgerodt-Type Dichloro(aryl)-3-Iodanes: A Structural Study

II

Cl

Cl

= Ph, CO2Et, Br, CF3

X-ray and solution-phase analysis

d+

Willgerodt-Type Reagents

ICl Clq1 q2

qT

S

pecial Topic

4408

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Synthesis 2019, 51, 4417–4424DOI: 10.1055/s-0039-1690034

L. WimbergerT. KratzT. Bach*Technische Universität München, Germany

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Photochemical Deracemization of Chiral Sulfoxides Catalyzed by a Hydrogen-Bonding Xanthone Sensitizer

5 mol%t = 8 h (MeCN)

S

O

NH

O

+S

O

NH

O

racemic mixture (0% ee)

S

O

NH

O

O

O

NH

O

N

O

hn (l = 366 nm)

98%55% ee

inversion

Paper

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Synthesis 2019, 51, 4425–4433DOI: 10.1055/s-0039-1690984

Y. JianM. ChenC. Yang*W. Xia*Harbin Institute of Technology (Shenzhen), P. R. of China

as

Nitroacenaphthene as a New Photocatalyst for the Synthesis of Sulfonyl Amidines

NO2

open airS

N3

O OS

N

O O

NEt2

blue LED

Ar Arsmall organic molecule

commercially available

recyclic utilization

Characteristics of the Catalyst

E1/2(*PC/PC–) = 1.11 V

+ NEt3

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Synthesis 2019, 51, 4434–4442DOI: 10.1055/s-0039-1690677

D. RoyG. Panda*CSIR-Central Drug Research In-stitute, India

Base-Mediated 1,6-Aza-Michael Addition of Heterocyclic Amines and Amides to para-Quinone Methides Leading to Meclizine-, Hydroxyzine- and Cetirizine-like Architectures

NaH

DMF, RT, 20–40 min

NuH

Nu = Heterocyclic amines (HCAs) & amides

Up to 100% atom economy Air and moisture tolerant One pot/Operationally Simple/Scalable Short reaction times Biologically important scaffold

Solvent

BaseNucleophile

para-quinonemethide

Unsymmetrical TRSMs

27 examplesup to 83% yield

R R

R1

O

R = tBu, i-PrR1 = H, Cl, Br, OMe,CF3, OCF3

Nu

OHRR

R1Unsymmetrical TRSMs

Paper

4434

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Synthesis 2019, 51, 4443–4451DOI: 10.1055/s-0039-1690198

M. MendozaR. EomC. SalasJ. Haynes-SmithK. L. Billingsley*California State University Fuller-ton, USA

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The Synthesis and Biological Evaluation of Indolactam Alkaloids

N

NH

HN

O

OH

EC50 = 142 nM to >10 µM

Paper

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Synthesis 2019, 51, 4452–4462DOI: 10.1055/s-0039-1690199

B. HeinzM. BalkenhohlP. Knochel*Ludwig-Maximilians-Universität München, Germany

as

Thiolation of Pyridine-2-sulfonamides using Magnesium Thiolates

TMPMgCl•LiCl(1.2 equiv)

THF, 0 °C, 2 h N SR

E1) E-X (1.2–1.6 equiv)THF, 0–25 °C

2) RSMgCl•LiCl(1.2 equiv)0–25 °C, 12 h

R = alkyl

N SN

O O

N S N

O O

MgCl•LiCl

19 examples50–95% yield

Paper

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Synthesis 2019, 51, 4463–4472DOI: 10.1055/s-0039-1690678

M. IsberaB. BognárG. Gulyás-FeketeK. KishT. Kálai*University of Pécs, HungarySzentágothai Research Centre, Hungary

Syntheses of Pyrazine-, Quinoxaline-, and Imidazole-Fused Pyrroline Nitroxides

N

N CONH2

NO

N

O O

ON

O

NN

Ph

N

NH

N

N

NH

O

O

O

SL-Pyrazinamide

SL-Lumazine

2–3 steps7 examples

15–39% overall yield

Paper

4463

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Synthesis 2019, 51, 4473–4486DOI: 10.1055/s-0039-1690621

S. R. MangaonkarF. V. Singh*VIT Institute, India

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Hypervalent Iodine(III)-Catalyzed Epoxidation of -Cyanostyrenes

ArR1

R2

PhI (10 mol%), Oxone (2.0 equiv)

TFA (2.4 equiv), CHCl3, rt, 60–90 min, ultrasonic bath

28 examples

R1 = CN, CO2Et; R2 = H, CN; Ar = Ph, 4-FC6H4, 2-ClC6H4, 4-ClC6H4, 2,3-(Cl)2C6H3, 3-BrC6H4, 4-BrC6H4, 4-NCC6H4, 3-HOC6H4, 4-MeC6H4, 3,4-(MeO)2C6H3, 3,4,5-(MeO)3C6H2, 2,3,4-(MeO)3C6H2, 4-(BnO)C6H4, 3-(HO)-4-(MeO)C6H3, 1-Naphthyl, 2-Naphthyl, 9-Anthryl

ArR1

R2

O

65–94%

Paper

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Synthesis 2019, 51, 4487–4497DOI: 10.1055/s-0037-1610726

G. JiangY. LinM. Cai*H. Zhao*Guangdong Pharmaceutical Uni-versity, P. R. of ChinaJiangxi Normal University, P. R. of China

as

Recyclable Heterogeneous Copper(II)-Catalyzed Oxidative Cyclization of 2-Pyridine Ketone Hydrazones Towards [1,2,3]Triazolo[1,5-a]pyri-dines

MCM-41-2N-Cu(OAc)2

(5 mol%)

33 examplesup to 94% yield

Recyclable copper catalyst!

EtOAc, r.t., airR

N

N

R1

NH2R

N N

N

R1

2.

EtOAc/EtOH (5:1), r.t., air

R

1. N2H4·H2O, AcOH (0.1 equiv)

EtOH, reflux, 6 h

N

R1

O RN N

N

R1

23 examplesup to 96% yield

MCM-41-2N-Cu(OAc)2

(5 mol%)

Paper

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Synthesis 2019, 51, 4498–4506DOI: 10.1055/s-0037-1610727

S. M. M. Rodrigues*D. PrevidiG. S. BavieraA. A. MatiasP. M. DonateUniversidade de São Paulo, Brazil

Niobium Pentachloride Mediated (Hetero)aromatic Aldehyde Friedel–Crafts Hydroxyalkylation with Arenes: An Efficient Strategy to Synthesize Triarylmethanes

H

ONbCl5 (1 equiv.)

DCM, rt

R

R

24 examples up to 99% yield

R = H, F, NO2, CH3, CF3, OCH3

X

X = various

X X

Paper

4498