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Synthesis of 4- to 7-membered Heterocycles by Ring Expansion pp 49–142Cite as

Ring Expansions of Activated Aziridines and Azetidines

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Part of the book series: Topics in Heterocyclic Chemistry ((TOPICS,volume 41))

Abstract

Facile construction of small and normal-sized, or more precisely, four to seven-membered aza-heterocyclic ring systems is always a challenging yet rewarding task for the synthetic organic chemists. Fortunately, activated aziridines and azetidines provide a direct and convenient access to this coveted molecular architectures through several elegant ring-expansion approaches. This chapter presents some of the illustrative and contemporary examples to demonstrate the synthetic diversity and efficiency of the ring-expansion strategies of activated aziridines and azetidines towards a vast array of small to normal-sized aza-heterocyclic moieties.

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Abbreviations

9-BBN:

9-Borabicyclo[3.3.1]nonyl

Ac:

Acetyl

AIBN:

Azobisisobutyronitrile

anhyd:

Anhydrous

aq:

Aqueous

Ar:

Aryl

BINAP:

2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl

BINOL:

1,1′-Bi-2-naphthol

BIPHEP:

2,2′-Bis(diphenylphosphino)-1,1′-biphenyl

Bn:

Benzyl

Boc:

tert-butyloxycarbonyl

Bts:

Benzothiazole-2-sulfonyl

Bu:

Butyl

Bz:

Benzoyl

cat:

Catalyst

Cbz:

Carboxybenzyl

COD:

Cyclooctadiene

Cp:

Cyclopropyl

c-Pr:

Cyclopropyl

CSA:

Camphorsulfonic acid

Cy:

Cyclohexyl

d:

Day(s)

DABCO:

1,4-Diazabicyclo[2,2,2]octane

dba:

Dibenzylideneacetone

DBU:

1,8-Diazabicyclo [5.4.0]undec-7-ene

DCC:

N,N′-Dicyclohexylcarbodiimide

DCE:

Dichloroethane

DCM:

Dichloromethane

de:

Diastereomeric excess

DEAD:

Diethyl azodicarboxylate

DHP:

2,3-Dihydropyran

DIAD:

Diisopropyl azodicarboxylate

DIBAL:

Diisobutylaluminum

DIPA:

Diisopropyl amine

DIPEA:

N,N-Diisopropylethylamine

DMA:

N,N-Dimethylacetamide

DMAP:

4-(Dimethylamino)pyridine

DME:

1,2-Dimethoxyethane

DMF:

N,N-Dimethylformamide

DMS:

Dimethyl sulfide

DMSO:

Dimethyl sulfoxide

DNP:

3,5-Dinitrophenyl

dppp:

1,3-Bis(diphenylphosphino)propane

dr:

Diastereomeric ratio

DROC:

Domino ring-opening cyclization

EDC:

N-(3-Dimethylaminopropyl)-N′-ethylcarbonate

EDG:

Electron-donating group

ee:

Enantiomeric excess

equiv.:

Equivalent(s)

Et:

Ethyl

EWG:

Electron-withdrawing group

h:

Hour(s)

Hex:

Hexyl

HMDS:

Bis(trimethylsilyl)amine, hexamethyldisilazane

HMPA:

Hexamethylphosphoramide

i-Pr:

Isopropyl

KHMDS:

Potassium hexamethyldisilazide, potassium bis(trimethylsilyl)amide

LA:

Lewis acid

LDA:

Lithium diisopropylamide

LHMDS:

Lithium hexamethyldisilazide, lithium bis(trimethylsilyl)amide

mCPBA:

m-Chloroperbenzoic acid

Me:

Methyl

Mes:

Mesityl, 2,4,6-trimethylphenyl

min:

Minute(s)

mol:

Mole(s)

MS:

Molecular sieves

Mtr:

4-Methoxy-2,3,6-trimethylbenzenesulfonyl

MW:

Microwave irradiation

NBD:

Norbornadiene

NBS:

N-bromosuccinimide

nm:

Nanometer

NMM:

N-Methylmorpholine

NMP:

N-methylpyridine

n-Pr:

n-Propyl

Ns:

(4-Nitrophenyl)sulfonyl

Nu:

Nucleophile

Oct:

Octyl

PG:

Protecting group

Ph:

Phenyl

phen:

1,10-Phenanthroline

Pr:

Propyl

p-Tol:

p-Tolyl

Pv:

Pivaloyl

py:

Pyridine

R:

Alkyl group

Rh2(esp)2 :

Bis[rhodium(α,α,α′,α′-tetramethyl-1,3-benzenedipropionic acid)]

rt:

Room temperature

SES:

2-(Trimethylsilyl)ethanesulfonyl

SN1:

Substitution nucleophilic (unimolecular)

SN2:

Substitution nucleophilic (bimolecular)

SPS:

Solid-phase synthesis

TBAF:

Tetrabutylammonium fluoride

TBAHS:

Tetrabutylammonium hydrogen sulfate

TBME:

tert-Butylmethyl ether

TBS/TBDMS:

tert-Butyldimethylsilyl

t-Bu:

tert-Butyl

TEA:

Triethylamine

TEBA:

Triethylbenzylammonium chloride

Tf:

Trifluoromethanesulfonyl (triflyl)

TFA:

Trifluoroacetic acid

THF:

Tetrahydrofuran

THP:

Tetrahydropyran-2-yl

TIPS:

Triisopropylsilyl

TMEDA:

Tetramethylethylenediamine

TMM:

Trimethylenemethane

TMS:

Trimethylsilyl

Tp:

Tetrazole

Ts:

Tosyl, 4-toluenesulfonyl

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Acknowledgments

MKG thanks CSIR, DST, and IIT Kanpur, India, for financial support. AB thanks CSIR, India, and SD and NC thank UGC, India, for research fellowships.

Dedication Dedicated to Prof. JoAnne Stubbe on the occasion of her 69th Birthday.

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  1. Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, UP, India

    Manas K. Ghorai, Aditya Bhattacharyya, Subhomoy Das & Navya Chauhan

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  1. Manas K. Ghorai
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  2. Aditya Bhattacharyya
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  3. Subhomoy Das
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Correspondence to Manas K. Ghorai .

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  1. Department of Sustainable Organic Chemistry and Technology, Faculty of Bioscience Engineering Ghent University, Ghent, Belgium

    Matthias D’hooghe

  2. Department of Chemistry, Hankuk University of Foreign Studies, Yongin-si, Korea (Republic of)

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Ghorai, M.K., Bhattacharyya, A., Das, S., Chauhan, N. (2015). Ring Expansions of Activated Aziridines and Azetidines. In: D’hooghe, M., Ha, HJ. (eds) Synthesis of 4- to 7-membered Heterocycles by Ring Expansion. Topics in Heterocyclic Chemistry, vol 41. Springer, Cham. https://doi.org/10.1007/7081_2015_159

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