Imprimatur:

Date, Signaturetc1119ss.fm 5/14/19

Reviews and Full Papers in Chemical Synthesis

2019Vol. 51, No. 11

June ISyn thesis

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Synthesis 2019, 51, 2237–2251DOI: 10.1055/s-0037-1611779

Z. RuanC. LiD. ShenS.-H. Huang*R. Hong*Shanghai Institute of Organic Chemistry (CAS), P. R of ChinaShanghai Institute of Technolo-gy, P. R of China

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FR901483: Synthetic Efficiency Remains a Challenge

Review

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Synthesis 2019, 51, 2252–2260DOI: 10.1055/s-0037-1611796

Z. Wang*State University of New York, USA

The Chemical Syntheses of Nannocystins

O

O

O

N

H

HHN

O

O

NH

Cl

Cl

HO

HO

O

O

ring-closing (alkyne) metathesis macrocyclization

via Pd chemistry

peptide coupling

peptide coupling

nannocystin A

S

hort Review

2252

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Synthesis 2019, 51, 2261–2277DOI: 10.1055/s-0037-1611773

K. HollandersB. U. W. Maes*S. Ballet*Vrije Universiteit Brussel, BelgiumUniversity of Antwerp, Belgium

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A New Wave of Amide Bond Formations for Peptide Synthesis S

hort Review

2261

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Synthesis 2019, 51, 2278–2286DOI: 10.1055/s-0037-1610877

A. TalkoD. AntoniakM. Barbasiewicz*University of Warsaw, Poland

as

Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates

SO2FLDA

Me3SiCl

THF–78 °C

SO2F SO2F

SiMe3 Me3Si SiMe3

or

up to 74%up to 86%

arenesulfonylfluorides

R R R

OSO2F

LDA

THF–78 °C

OH

SO2For

R R R

arylfluoro-sulfates anionic

thia-Friesrearrangement

Feature

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Synthesis 2019, 51, 2287–2292DOI: 10.1055/s-0037-1611726

Y. QianJ. SoS.-Y. JungS. HwangM.-J. Jin*S. E. Shim*Inha University, South Korea

A Graphene Oxide Nanosheet Supported NHC–Palladium Complex as a Highly Efficient and Recyclable Suzuki Coupling Catalyst

Paper

2287

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Synthesis 2019, 51, 2293–2304DOI: 10.1055/s-0037-1611747

G. Perin*P. C. NobreD. H. MailahnM. S. SilvaT. BarcellosR. G. JacobE. J. LenardãoC. SantiJ. A. RoehrsUniversidade Federal de Pelotas (UFPel), Brazil

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Synthesis of 4-Organoselanyl-1H-pyrazoles: Oxone®-Mediated Electrophil-ic Cyclization of ,-Alkynyl Hydrazones by Using Diorganyl Diselenides

R1

R2

N

HN

R3

RSeSeR Oxone®

ethanol, 70 °Copen flask

N NR2

R1SeR

+

1a–k2a–g

3a–qR3

mild reaction condition

metal- and halogen-free

easy to scale-up77Se NMR and HRMS studies

good yield, 17 examples

Paper

2293

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Synthesis 2019, 51, 2305–2310DOI: 10.1055/s-0037-1610867

Y. Ichikawa*T. YamasakiK. NakanishiY. UdagawaS. HosokawaT. MasudaKochi University, Japan

as

Bioinspired Synthesis of the Central Core of Halichonadin H: The Passerini Reaction in a Hypothetical Biosynthesis of Marine Natural Products

O

NH

HO

NH

H

OH

halichonadin H

O

NH

O

NH

OH

NC

O

NH

OH

Passerini reaction 2)

3) hydrolysisHCHO

1) oxidation

Passerini reaction

Paper

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Synthesis 2019, 51, 2311–2317DOI: 10.1055/s-0037-1611765

V. P. AndradeM. MittersteinerH. G. BonacorsoC. P. FrizzoM. A. P. MartinsN. Zanatta*Universidade Federal de Santa Maria, Brazil

Regioselective Synthesis of 5-(Trifluoromethyl)[1,2,4]triazolo[1,5-a]pyrimidines from -Enamino Diketones

R

O O

CF3

N

NH

N

H2N

N

N

CF3

NN

O

R

R1

68–94% yields

R = aryl, heteroarylR1 = H, SMe, CO2H

R1

Me2N

New starting material for triazolopyrimidine synthesis

High yielding and easy purification products

Access to a new pattern of substitution on the pyrimidine ring

Paper

2311

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Synthesis 2019, 51, 2318–2322DOI: 10.1055/s-0037-1610865

S. TafukuT. FukudaK. ChibaY. Kitano*Tokyo University of Agriculture and Technology, Japan

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A New Method for the Preparation of Bis(alkylamino)maleonitriles from Aliphatic Isocyanides with TMSCN and Bi(OTf)3

TMSCN

HN

CC

NH

NC CN

Bi(OTf)3NCR

R = tert-alkyl

R R

CH2Cl2, rt

TMSOTf

13 examples

up to 43% yield• In a single step

• Highly functional-group tolerant

• Simple and mild conditions

Paper

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Synthesis 2019, 51, 2323–2330DOI: 10.1055/s-0037-1610869

N. Sakai*H. MaedaY. Ogiwara Tokyo University of Science (RIKADAI), Japan

as

Copper-Catalyzed Three-Component Coupling Reaction of Aryl Iodides, a Disilathiane, and Alkyl Benzoates Leading to a One-Pot Synthesis of Alkyl Aryl Sulfides

I

FG Ar Me3SiS

SiMe3+

O

PhOR+

cat. Cubase

FG Ar

SR

alkyl aryl sulfide

23 examplesthree-component coupling reaction via a single steputility of a disilathiane as a sulfur sourceexpansion of an alkyl source to an alkyl benzoate

Paper

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Synthesis 2019, 51, 2331–2338DOI: 10.1055/s-0037-1610868

Y. Su*L. CaoY. ShiY. FengW. XueG. CaoK.-H. WangD. HuangC. HuoY. HuNorthwest Normal University, P. R. of China

Trichloroisocyanuric Acid Induced Chlorine Radical Cascade Chlorination/Carbocyclization of Acrylamides: Constructing Chlorinated Oxindoles by C–Cl and C–C Bond-Forming Reactions

R1

N

R2

O

R3

MeCN, rtR1

N

R2

O

ClCl R3R4 R4

N

N

NCl Cl

Cl

O O

O

TCCA

Cl" "

Chlorine-radical-induced cyclization

Without metal or additional oxidant

Efficient C–Cl and C–C bond formation

23 examples30–80% yield

R1 = Cl, Br, F, CF3, Me, EtR2 = Me, Et, Ph, Bn, CH2CO2MeR3 = Me, Ph, Bn, CH2OH, OTBS, OAcR4 = H, Ph

Paper

2331

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Synthesis 2019, 51, 2339–2350DOI: 10.1055/s-0037-1610875

X. ZuoS. ChenS.-W. XuS.-Q. ChangX.-L. Liu*Y. ZhouW.-C. YuanGuizhou University, P. R. of China

Syn thesis

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Highly Efficient, Catalyst-Free, Diastereoselective, Diversity-Oriented Synthesis of Dihydrocoumarin–Pyrrolidine–Spirooxindoles Bearing Three Contiguous Stereocenters

catalyst-free, rt

NO

R1

NCS O O

EWG

N O

HN O

OS

R1CH3CN, 15 min

R2 R2

R3

R3EWG

catalyst-free, rt

O O

CO2H

NO

HNO

OS

R1CH3CN, 15 min

R2

R3

R3

18 examples,up to 92% yield and >20:1 dr

15 examples,up to 87% yield and 19:1 dr

EWG = CO2R or CN

Paper

2339

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Synthesis 2019, 51, 2351–2358DOI: 10.1055/s-0037-1610695

S. J. MattinglyF. Wuest*R. Schirrmacher*University of Alberta, Canada

as

Synthesis of 2-Fluoroacetoacetic Acid and 4-Fluoro-3-hydroxybutyric Acid

Paper

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Synthesis 2019, 51, 2359–2370DOI: 10.1055/s-0037-1610685

D. MunE. KimS.-G. Kim*Kyonggi University, Republic of Korea

Palladium-Catalyzed Decarboxylative [4+2] Cycloaddition of Vinyl Ben-zoxazinanones with Cyclic N-Sulfimines: Stereoselective Synthesis of Benzosulfamidate-Fused Tetrahydroquinazolines

46–87% yieldup to >30:1 drup to 98% ee

NS

O

O

R1

N

O

Ts

O

R2

N

Ts

R2N O

S

O O

O

R1

Pd2(dba)3 (5 mol%)

L (10 mol%)toluene, –10 °C

O

O

P N

L

up to 98% yieldup to >30:1 dr

NH

R2N O

S

O O

R1

NH

O

O

R2

Pd(PPh3)4(5 mol%)CH2Cl2, rt

Paper

2359

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Synthesis 2019, 51, 2371–2378DOI: 10.1055/s-0037-1610696

R. ChatterjeeS. SantraG. V. ZyryanovA. Majee*Visva-Bharati (A Central Univer-sity), India

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Vinylation of Carbonyl Oxygen in 4-Hydroxycoumarin: Synthesis of Heteroarylated Vinyl Ethers

Conditions: BF3·OEt2 (20 mol%), neat, 80 °C, 10 min

R

O O

OH

O O

O

R

O-Vinylation of 4-Hydroxycoumarin

R1

R = aryl, alkyl, heteroaryl

19 examples

73–86% yields

R1

R'

R' = HR' = Me

O O

O

Ph

Me

Major

(E/Z = 3:1)

H

Paper

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Synthesis 2019, 51, 2379–2386DOI: 10.1055/s-0037-1610698

G. G. ZakirovaD. Y. MladentsevN. E. Borisova*Lomonosov Moscow State University, Russian Federation

as

Palladium-Catalyzed C–P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides

Pd-catalyzed cross-coupling

P

R

O

RH

N

N N

P P

P PO O

O OR

R

R

R

R

R

R

R

N

PR'

R'

PO

R R

O

RR

12 examples35–95%

9 examples35–91%

8 examples68–98%

7 examples75–98%

PyCl2

BipyCl2

PhenCl2

ArX

HetArX

R = alkyl, aryl; X = I, Br, Cl;R' = EWG, EDG

Paper

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Synthesis 2019, 51, 2387–2396DOI: 10.1055/s-0037-1612253

C. Cimarelli*F. NavazioF. V. RossiF. Del BelloE. MarcantoniUniversity of Camerino, Italy

Activation of Primary Amines by Copper(I)-Based Lewis Acid Promot-ers in the Solventless Synthesis of Secondary Propargylamines

O

HR2

Ph

R2

HNR1

Ph

N

HR2

R1

iii)

R1NH2ii)

+

O

HR2

i)+Ph

Method B: 20 examples up to 95% yieldii) MgSO4, CeCl3•7H2O (30 mol%), solventless, N2, r.t., 0.25 hiii) CuI (30 mol%), solventless, N2, 40 °C

Method BMethod A

R1NH2

Method A: 9 examples up to 62% yieldi) CuSO4 (30 mol%)/NaI (60 mol%), PhCOOH (5 mol%), solventless, N2, 80 °C

1a–f 1a–f

2a–p 2a–p

Paper

2387

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Synthesis 2019, 51, 2397–2401DOI: 10.1055/s-0037-1610862

Y. Zhu§

Q. Wang§

H. LuoZ. WangG. Zhang*Y. Yu*Zhejiang University, P. R. of China

Syn thesis

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A Facile and Efficient Approach for the Synthesis of 3-Aryl-4-hydroxy-1,3-thiazolidin-2-ones

R N3

O+

S

S

HO

OH MeCN

80 °C, 21 h

NS

O

R

HO

72–90%10 examples

Paper

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Synthesis 2019, 51, 2402–2408DOI: 10.1055/s-0037-1612279

Z.-R. Guan S. Liu Z.-M. LiuM.-W. Ding*Central China Normal University, P. R. of China

as

One-Pot Three-Component Synthesis of Pyrrolidin-2-ones via a Sequential Wittig/Nucleophilic Addition/Cyclization Reaction

Ph3P

OR1O

OR1

OC

OR1O

OR1

OR2N

1. R3NH2

2. R1ONa NR2N O

R3

O

R1OR2NCO

Paper

2402

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Synthesis 2019, 51, 2409–2429DOI: 10.1055/s-0037-1611736

J. BaumgartnerR. G. Bergman*B. KayserT. P. KlupinskiY. K. ParkK. P. C. Vollhardt*M. J. WestB. ZhuUniversity of California at Berkeley, USA

The Quest for Double Vicinal C–H Bond Activation on the (η5:η5-Fulvalene)diiridium Platform: Syntheses and Structures of (η5:η5-Fulvalene)Ir2(ortho-μ-C6H4)(CO)2 (Ir–Ir) and Related Complexes

Ir

OCCO

IrH CO

R

R

R

R

IrH

CO

R

R

IrH

OC

R

R

Ir IrOC CO

Ir IrOC CO

R

R

R

R

R

R

R

R

C6H6, hnIrIr

OCCOCOOC

R

R

R

R

– H2

– H2C6H6, hn

R = H, t-Bu

hn

hn

Paper

2409

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Synthesis 2019, 51, 2430–2434DOI: 10.1055/s-0037-1612415

F. Fache*I. de AzpiazuB. PelotierO. PivaC. GozziUniversité Claude Bernard Lyon 1, France

Syn thesis

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Green Access to -Haloalkyl and -Halobenzyl Esters, Versatile Intermediates for the One-Pot Two-Step Synthesis of O,O′-Diacyl Acetals Using Zinc-Based Ionic Liquid Catalyst

R H

R' Cl

O

O

+BMIZnCl3

R Cl

O R'

O

O

R"O

14 examplesup to 92% yield

(10 mol%) R

O R'

O

R" OH

O

R, R' = alkyl, aryl

Paper

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