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. 2018 May;7(5):852-864.
doi: 10.1002/ajoc.201800091. Epub 2018 Mar 25.

Ammonium Ylide Mediated Cyclization Reactions

Lukas Roiser  1 , Katharina Zielke  1 , Mario Waser  1
Affiliations

Ammonium Ylide Mediated Cyclization Reactions

Lukas Roiser et al. Asian J Org Chem. 2018 May.

Abstract

The use of readily accessible ammonium ylides for (asymmetric) transformations, especially cyclization reactions, has received considerable attention over the past two decades. A variety of highly enantioselective protocols to facilitate annulation reactions have recently been introduced as an alternative to other common methods including S-ylide-mediated strategies. It is the intention of this short review to provide an introduction to this field by highlighting the potential of ammonium ylides for (asymmetric) cyclization reactions as well as to present the limitations and challenges of these methods.

Keywords: asymmetric synthesis; cyclization; heterocycles; small ring systems; ylides.

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Conflict of interest statement

Conflict of interest The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
General representation of different classes of ylides and N-ylides (EWG = electron-withdrawing group, PG = protecting group).
Scheme 2
Scheme 2
Ylide-mediated three-membered ring formation.
Scheme 3
Scheme 3
First examples of ammonium ylide mediated cyclopropanation reactions (d.r. = diastereomeric ratio).
Scheme 4
Scheme 4
Gaunt’s seminal report of the use of catalytic quantities of a tertiary amine to promote ammonium ylide mediated cyclopropanations.
Scheme 5
Scheme 5
Asymmetric intra- and intermolecular ammonium ylide mediated cyclopropanation reactions.
Scheme 6
Scheme 6
Application of Gaunt’s asymmetric ammonium ylide mediated cyclopropanation for natural product syntheses (TBDPS = tert-butyldiphenylsilyl).
Scheme 7
Scheme 7
Ammonium ylide reaction with lactam and lactone acceptors (PG = protecting group, Tos = para-toluenesulfonyl).
Scheme 8
Scheme 8
Azetidinium and pyrrolidinium ylides for cyclopropanations (OTf = trifluoromethanesulfonate, LiHMDS = lithium hexamethyldisilazide).
Scheme 9
Scheme 9
Ammonium ylide mediated syntheses of fluorine-containing cyclopropanes 35 and 37 (DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene).
Scheme 10
Scheme 10
Ammonium ylide mediated asymmetric spirocyclopropanation of p-quinone methides 38.
Scheme 11
Scheme 11
Initial reactions of ammonium ylides with carbonyl compounds.
Scheme 12
Scheme 12
First ammonium ylide mediated epoxidation using cyanide-stabilized ylides.
Scheme 13
Scheme 13
Benzylic ammonium ylides for epoxidations and illustration of the importance of the amine leaving group on the reaction outcome.
Scheme 14
Scheme 14
Asymmetric benzylic ammonium ylide mediated epoxidation by using brucine as a chiral amine leaving group.
Scheme 15
Scheme 15
Azetidinium ylide mediated epoxidation.
Scheme 16
Scheme 16
Carbonyl-stabilized ammonium ylides for (racemic) epoxidations.
Scheme 17
Scheme 17
Chiral auxiliary approaches for amide-stabilized ammonium ylide mediated epoxidations.
Scheme 18
Scheme 18
Ammonium ylide mediated aziridination by using strained ammonium salt 30.
Scheme 19
Scheme 19
Carbonyl-stabilized ammonium ylide mediated aziridinations (DCM = dichloromethane).
Scheme 20
Scheme 20
Ammonium ylide mediated azetidine synthesis.
Scheme 21
Scheme 21
Ammonium ylide mediated synthesis of 2,3-dihydrofuranes 76 and pyrroles 80.
Scheme 22
Scheme 22
Chiral ammonium ylide mediated asymmetric synthesis of isoxazoline N-oxides.
Scheme 23
Scheme 23
Catalytic asymmetric [4+1] annulation that employs chiral ammonium ylides.
Scheme 24
Scheme 24
Asymmetric ammonium ylide mediated dihydrobenzofuran syntheses.
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