The Aza‐Achmatowicz Reaction: Facile Entry into Functionalized Piperidinones

Pijl, Ferdi van der; Delft, Floris L. van; Rutjes, Floris P. J. T.

doi:10.1002/ejoc.201500321

Cited by 55 publications

(28 citation statements)

References 77 publications

(60 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Over the past decades, the Achmatowicz‐type ring expansion – the oxidative conversion of α‐heterosubstituted furfuryl derivatives to six‐membered O‐ or N‐heterocyclic building blocks – has become a valuable tool in modern synthetic organic chemistry . Both the easy access to suitable heteroaromatic Achmatowicz substrates as well as the broad range of follow‐up chemistry offered by the pyranone or piperidinone products make this transformation an attractive instrument in the synthesis of complex natural products and biologically active agents.…”

Section: Introductionmentioning

confidence: 99%

Chloroperoxidase‐Catalyzed Achmatowicz Rearrangements

et al. 2018

View full text Add to dashboard Cite

Chloroperoxidase from Caldariomyces fumago catalyzes the selective oxidation of furfuryl alcohols in an Achmatowicz‐type ring expansion. In combination with glucose oxidase as oxygen‐activating biocatalyst, a purely enzymatic, aerobic protocol for the synthesis of 6‐hydroxypyranone building blocks is obtained. Thanks to an only modest stereochemical bias of the oxygenating heme protein, optically active alcohols of either configuration are converted without a significant mismatch opening up opportunities for enantioselective multienzymatic cascades. Balancing the oxidase‐driven aerobic activation, extended enzyme half‐lives and productive conversion of poorly soluble and slowly reacting substrates can be achieved with high yields of the six‐membered O‐heterocycles.

show abstract

Section: Introductionmentioning

confidence: 99%

Chloroperoxidase‐Catalyzed Achmatowicz Rearrangements

et al. 2018

View full text Add to dashboard Cite

show abstract

“…7 Another review by Rutjes and co-workers details an aza-Achmatowicz reaction leading to the synthesis of functionalized piperidones. 8 …”

Section: Introductionmentioning

confidence: 99%

“…Their subsequent acidic hydrolysis provides the cis -dicarbonyl alcohols ( 47 ), which immediately rearranges/cyclizes into the corresponding hydroxy pyranones 48 upon ring-closure. 8 …”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Achmatowicz reaction and its application in the syntheses of bioactive molecules

Ghosh

Brindisi

2016

RSC Adv.

View full text Add to dashboard Cite

Substituted pyranones and tetrahydropyrans are structural subunits of many bioactive natural products. Considerable efforts are devoted toward the chemical synthesis of these natural products due to their therapeutic potential as well as low natural abundance. These embedded pyranones and tetrahydropyran structural motifs have been the subject of synthetic interest over the years. While there are methods available for the syntheses of these subunits, there are issues related to regio and stereochemical outcomes, as well as versatility and compatibility of reaction conditions and functional group tolerance. The Achmatowicz reaction, an oxidative ring enlargement of furyl alcohol, was developed in the 1970s. The reaction provides a unique entry to a variety of pyranone derivatives from functionalized furanyl alcohols. These pyranones provide convenient access to substituted tetrahydropyran derivatives. This review outlines general approaches to the synthesis of tetrahydropyrans, covering general mechanistic aspects of the Achmatowicz reaction or rearrangement with an overview of the reagents utilized for the Achmatowicz reaction. The review then focuses on the synthesis of functionalized tetrahydropyrans and pyranones and their applications in the synthesis of natural products and medicinal agents.

show abstract

“…Finally, derivatization of the product based on the 2-methoxyfuryl moiety was performed ( Scheme 2 ). The cleavage of the furan ring of 8a proceeded smoothly under Achmatowicz type reaction conditions, 21 and subsequent chemoselective reduction of the keto moiety under Luche conditions resulted in the formation of butenolide 10 in a good yield over two steps. In the course of the derivatization, the loss of enantiomeric purity did not occur.…”

mentioning

confidence: 99%