Imprimatur:

Date, Signaturetc1819ss.fm 8/15/19

Reviews and Full Papers in Chemical Synthesis

2019Vol. 51, No. 18

September IISyn thesis

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Synthesis 2019, 51, 3369–3396DOI: 10.1055/s-0037-1611844

J. G. Sośnicki*T. J. IdzikWest Pomeranian University of Technology, Poland

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Pyridones – Powerful Precursors for the Synthesis of Alkaloids, Their Derivatives, and Alkaloid-Inspired Compounds

N O

R

R'

2-Pyridones

N

MeO2H2C

H

NH

(+)-Andranginine

N N

O

O

OHO

Et

Camptothecin

NH

NO

(±)-Cytisine

N

NH

MeO

H H

IbogaineIrinotecan (CPT-11)

N N

O

O

OHO

Et

N

O

N

O N

O

N

Me

H

Me

(+)-Hosieine A

Review

3369

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Synthesis 2019, 51, 3397–3409DOI: 10.1055/s-0037-1611891

A. S. Gazizov*A. V. SmolobochkinR. A. TurmanovM. A. PudovikA. R. BurilovO. G. SinyashinArbuzov Institute of Organic and Physical Chemistry, Russian Federation

Synthesis of Phosphaproline Derivatives: A Short Overview

NP

Y

O

X

G

Y

N

R

R

NRN

N

N

N

ArNH

CO2H

NOR

XH

pyrrolidinederivatives

phosphorylation

synthesis fromacyclic

precursors

XYP(O)H

(RO)3P

HNX G H2N

O

R

+

HNOR

HN

G RG

XYP(O)H

P

P

P

S

hort Review

3397

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Synthesis 2019, 51, 3410–3418DOI: 10.1055/s-0037-1611567

M.-Y. Chang*K.-X. LaiKaohsiung Medical University, TaiwanKaohsiung Medical University Hospital, Taiwan

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Palladium(II) Acetate Mediated Dimerization/Cycloisomerization of 2-Sulfonyl-4-alkynones: Synthesis of trans-1,2-Difurylethylenes

one-pot atom-economic synthesis easy operational open atmosphere

Pd(OAc)2, PPh3

Na2CO3, EtOH2

Ar O

SO

OR

OAr

SO R

OAr O

SO

OR

+ 4 H2

21 examples 8–78% yieldtrans-only 1,2-difurylethylenes

Paper

3410

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Synthesis 2019, 51, 3419–3430DOI: 10.1055/s-0039-1689973

M.-Y. Chang*Y.-H. ChenH.-Y. ChenKaohsiung Medical University, Taiwan, ROCKaohsiung Medical University Hospital, Taiwan

as

Copper(II) Acetate Mediated Synthesis of 3-Sulfonyl-2-aryl-2H-chromenes

O

OH O Ar

S

O

O RO

Ar' Ar'

S

Ar

O

O

R

+

O Ar

S

O

O RO

Ar'

nBu

OHCu(OAc)2

PyBOPDMAP

easy operation

inexpensive copper salt

high yield

one-pot two-step route

37 examples

nBuBr

Paper

3419

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Synthesis 2019, 51, 3431–3442DOI: 10.1055/s-0039-1690001

M. J. Mphahlele*T. O. OlomolaUniversity of South Africa, South Africa

Synthesis and Transformation of 5-Acetyl-2-aryl-6-hydroxybenzo-furans into Furanoflavanone Derivatives

Paper

3431

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Synthesis 2019, 51, 3443–3450DOI: 10.1055/s-0039-1689937

A. S. SinghA. K. AgrahariS. K. SinghM. S. YadavV. K. Tiwari*Banaras Hindu University, India

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An Improved Synthesis of Urea Derivatives from N-Acylbenzotriazole via Curtius Rearrangement

N

O

NN

NH

NH

Otoluene

NH2 30 examples

.

TMSN3

Et3N, r.t.

O

N3NCO

+110 °C

Advantage: One-pot Easy workup Short reaction time Metal-free Applicable for synthesis of symmetric/unsymmetric/cyclic/N-acyl urea

=yields up to 99%

aryl, alkyl

Paper

3443

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Synthesis 2019, 51, 3451–3461DOI: 10.1055/s-0039-1690099

Y.-L. Hu B.-B. Gou J. WangM. ZhaoJ.-L. LiuJ. Chen*L. Zhou*Northwest University, P. R. of China

as

N-Heterocyclic Carbene Catalyzed Stereoselective Synthesis of 2-Nitro-thiogalactosides

Cs2CO3 (0.1 equiv)

O

NO2

OBn

BnO

SRO

NO2

OBn

BnO

PO PO

DCM, r.t., 24 h

27 examples up to 95%

yield

RSH+

N NMes Mes

Cl

(0.15 equiv)

R = alkyl, a:b = 4:1 to 1:0R = aryl, a:b > 25:1

Paper

3451

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Synthesis 2019, 51, 3462–3470DOI: 10.1055/s-0037-1611539

S. GiofrèE. M. Beccalli*F. FoschiC. La RosaL. Lo PrestiM. S. ChristodoulouUniversità degli Studi di Milano, Italy

Chemo- and Regioselective Palladium(II)-Catalyzed Aminoarylation of N-Allylureas Providing 4-Arylmethyl Imidazolidinones

Paper

3462

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Synthesis 2019, 51, 3471–3476DOI: 10.1055/s-0037-1611566

I.-S. MyeongC. JungW.-H. Ham*Sungkyunkwan University, Republic of KoreaYonsung Fine Chemicals Co., Ltd., Republic of Korea

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Total Syntheses of (–)-7-epi-Alexine and (+)-Alexine Using Stereo-selective Allylation

N O

TBSO

TBSO

Ph

OHCbzN

TBSO OMOM

TBSO

OHOH

CbzN

TBSO OMOM

TBSO OH

N

HO

HO

HO H OH

CbzN

TBSO OMOM

TBSO OH

N

HO

HO

HO H OH

(−)-7-epi-alexine

(+)-alexine

Paper

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Synthesis 2019, 51, 3477–3484DOI: 10.1055/s-0037-1611850

F.-P. Liu H.-P. Zhao S. TanX. LuD.-L. Mo*Guangxi Normal University, P. R. of China

as

Preparation of 2-(3-Methyleneindolin-2-yl)phenols via Sodium Hydride Promoted C–C/C–O Bond Cleavage

O

NHR2

CHO

R1NaH

OH

NHR2

R1

MeCN, rt

21 examples51–95% yield

R3R3

·Inexpensive and green NaH ·Tandem C–C/C–O bond cleavage

·Good functional group tolerance ·New application of NaH as a nucleophile

Paper

3477

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Synthesis 2019, 51, 3485–3490DOI: 10.1055/s-0039-1689971

R. R. Gataullin*E. S. MescheryakovaR. M. SultanovA. A. FatykhovL. M. KhalilovUfa Institute of Chemistry of the Russian Academy of Sciences, Russian Federation

An Unexpected Dihalogenation/Dehydrogenation Product Derived via Iodolactonization of an N-Tosyl-N-[6-(2-cyclopenten-1-yl)-2-methyl-phenyl]glycine

H

N

CH3 CH2CO2H

syn/anti

Ts

N

O

I

H

O

TsH3C

I2, K2CO3

CH2Cl2N

O

I

O

TsH3C

I1 3

6 9

10

113a11b

+

Paper

3485

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Synthesis 2019, 51, 3491–3498DOI: 10.1055/s-0039-1689916

P. Zlatoidský*E. MartinelliE. SvenssonA. Pruvost AstraZeneca, Sweden

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A Facile Access to Novel (5+5) Annellated Heterocycles: Synthesis of a Furopyrrole, an Imidazoimidazole and a Pyrroloimidazole

HNN

N

ON

EtOOC

N

ON

NNHBr

N absabs

O

HN

O

ON

EtOOC

OBr

O

4 steps

2, Total yield: 9.6%

6 steps

4 steps3, Total yield: 4.3%

4, Total yield: 8.45%

Paper

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Synthesis 2019, 51, 3499–3505DOI: 10.1055/s-0039-1689936

Z. XiaoA.-Y. Peng*Sun Yat-sen University, P. R. of China

as

Palladium(II) Acetate Catalyzed Cyclization–Coupling of (o-Ethynyl-phenyl)phosphonic Acid Monoesters with Allyl Halides

R1 PO

OH

OEt

R2

+ X

Pd(OAc)2 (10 mol%)

THF, r.t., 6 hP

O

R2

O OEtR1

R3

R3

R1 = H, MeO, Cl; R2 = H, aryl, alkylR3 = H, Me, Br; R4 = H, CH3; X = Br, Cl

up to 93% yield18 examples

R4

R4

Paper

3499

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Synthesis 2019, 51, 3506–3510DOI: 10.1055/s-0037-1611870

Q. LiuG.-x. HuangM.-j. LiuF.-E. Chen*Fudan University, P. R. of ChinaShanghai Engineering Center of Industrial Asymmetric Catalysis for Chiral Molecules, P. R. of China

A Concise Total Synthesis of (±)-Camptothecin

N Cl

O

O

O

O

NHBoc

N

NBoc

O

O

OO

+

dominoHeck/aza-Michael addtion 4 steps N

NO

O

OH O

Paper

3506

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Synthesis 2019, 51, 3511–3519DOI: 10.1055/s-0037-1611888

B. ZhouS. GuoZ. FangZ. YangC. LiuW. HeN. ZhuX. LiK. Guo*Nanjing Tech University, P. R. of China

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KI-Promoted Oxidative Coupling of Styrenes with Indoles under Metal-Free Conditions: Facile Access to C-3 Dicarbonyl Indoles

Metal freeHigh atom economyInexpensive raw chemicals Good to excellent yieldsShort reaction time

19 examples up to 91% yield

ArN

R2N

R2

Ar

OO

R1R1

+

KI/TBHP DMSO

130 °C, 4 h

Paper

3511

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Synthesis 2019, 51, 3520–3528DOI: 10.1055/s-0037-1611871

Y.-t. RuanY.-p. ChenL.-h. GuY. LuoZ. YangL. He*Sichuan University, P. R. of China

as

Preparation of Imidazole Derivatives via Bisfunctionalization of Alkynes Catalyzed by Ruthenium Carbonyl

PhI(OAc)2

Ru3(CO)12

tolueneR1

OAc

OAc

R2

(NH4)2CO3 NNH

R1

R2

R

16 examplesup to 82% yield

8 examplesup to 84% yield

R1 R2

R2 = HRCH2OH

Paper

3520

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Synthesis 2019, 51, 3529–3535DOI: 10.1055/s-0037-1611838

C. Osei Akoto*J. D. RainierUniversity of Utah, USA

Concise Seven-Membered Oxepene/Oxepane Synthesis – Structural Motifs in Natural and Synthetic Products

OTBDPSO

MeO

OTBDPSOH

MeOH

1. ''Ru''

diene oxepene

2. Rh(PPh3)3Cl

1. DMDO, CH2Cl2

2. MgBr

THF, (92%)

OTBDPSOH

MeOH

OH

oxepane

Grubbs II catalyst

isomerized product

Paper

3529

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Synthesis 2019, 51, 3536–3544DOI: 10.1055/s-0037-1611480

A. B. BellanP. Knochel*Ludwig-Maximilians-Universität München, Germany

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Steric-Hindrance Triggered Remote Lithiations of Bulky Silyl-Substituted Arenes

FG

SiEt3Et3Si

H

nBuLi•PMDTA

nhexane, –10 to 25 °C, 6 h

FG

SiEt3Et3Si

Li

E-X

FG

SiEt3Et3Si

E

16 examples, up to 59% yield

Paper

3536

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Synthesis 2019, 51, 3545–3555DOI: 10.1055/s-0039-1690101

X. BaiF. AiolfiM. CettolinU. PiarulliA. Dal CorsoL. Pignataro*C. Gennari*Università degli Studi di Milano, Italy

as

Hydrogen-Borrowing Amination of Secondary Alcohols Promoted by a (Cyclopentadienone)iron Complex

Paper

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Synthesis 2019, 51, 3556–3566DOI: 10.1055/s-0037-1611540

S. AounP. SierockiJ. Lebreton*M. Mathé-Allainmat*Université de Nantes, France

Linear and Convergent Syntheses of Bifunctional Hydroxy-Bisphos-phonic Compounds as Potential Bone-Targeting Prodrugs

ON

N NO

O

Me

HBcat

R2O3P

R2O3PHO

R = H or Me

P(OSiMe3)3

OO

N

O

Me

OO

N3 Me

O

+

"Click"

HO

3

5 steps

Bifunctional HBP compounds3 steps

Me

Me

Me

Me Me

Me

Me

HO

O

32O

ON

O

Me

Me

Me

Me

P

P

32

HO

HO OHO

HO

OHO

Linear synthesis

Convergent synthesis P

PHO

HO

OHO

OHHOO

32

OH

Paper

3556