The cerium (III) mediated reaction of trimethylsilylmethyl magnesium chloride with esters and lactones: The efficient synthesis of some functionalised allylsilanes of use in annulation reactions

Lee, Thomas V.; Channon, Julia A.; Cregg, C.; Porter, John R.; Roden, F. S.; Yeoh, Helena T-L.

doi:10.1016/s0040-4020(01)89114-6

Cited by 66 publications

(17 citation statements)

References 12 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This approach demands a structural modification of the tri-component adduct (−)- 37 , which, given the great flexibility of the ARC protocol, pleasingly only required a simple modification of the epoxide linchpin (−)- 25 . To test this hypothesis, known epoxide 47a 28 (Scheme 8A) possessing a terminal olefin was synthesized from commercially available aldehyde 47b 29 via treatment with chloromethyl lithium 20 and then subjected to Jacobsen hydrolytic kinetic resolution 21 to furnish the desired enantiomer (−)- 47 . Importantly, the diol byproduct ( 47c ) from the Jacobsen resolution could also be readily converted to the desired epoxide (−)- 47 in 65% yield via a three-step reaction sequence.…”

Section: Resultsmentioning

confidence: 99%

Synthetic Access to the Mandelalide Family of Macrolides: Development of an Anion Relay Chemistry Strategy

et al. 2018

View full text Add to dashboard Cite

The mandelalides comprise a family of structurally complex marine macrolides that display significant cytotoxicity against several human cancer cell lines. Presented here is a full account on the development of an Anion Relay Chemistry (ARC) strategy for the total synthesis of (-)-mandelalides A and L, the two most potent members of the mandelalide family. The design and implementation of a three-component type II ARC/cross-coupling protocol and a four-component type I ARC union permits rapid access respectively to the key tetrahydrofuran and tetrahydropyran structural motifs of these natural products. Other highlights of the synthesis include an osmium-catalyzed oxidative cyclization of an allylic 1,3-diol, a mild Yamaguchi esterification to unite the northern and southern hemispheres, and a late-stage Heck macrocyclization. Synthetic mandelalides A and L displayed potent cytotoxicity against human HeLa cervical cancer cells (EC, 1.3 and 3.1 nM, respectively). This synthetic approach also provides access to several highly potent non-natural mandelalide analogs, including a biotin-tagged mandelalide probe for future biological investigation.

show abstract

Section: Resultsmentioning

confidence: 99%

Synthetic Access to the Mandelalide Family of Macrolides: Development of an Anion Relay Chemistry Strategy

et al. 2018

View full text Add to dashboard Cite

show abstract

“…Ketone 15 could then be obtained in 79% yield over three steps using conventional functional group interconversion reactions, including protection, Weinreb amide formation, and methylation. Ketone 15 was resistant to conversion into the requisite allylsilane moiety using a Peterson-type olefination reaction [41]. However, 15 was converted into enol triflate 16 upon treatment with Comin's reagent [42], followed by deprotection and the allylsilane moiety introduction via a Pd-catalyzed coupling reaction.…”

Section: Molecules 2020 25 1175 4 Of 16mentioning

confidence: 99%

Synthesis of Tetrabenazine and Its Derivatives, Pursuing Efficiency and Selectivity

Paek

2020

Molecules

View full text Add to dashboard Cite

Tetrabenazine is a US Food and Drug Administration (FDA)-approved drug that exhibits a dopamine depleting effect and is used for the treatment of chorea in Huntington’s disease. Mechanistically, tetrabenazine binds and inhibits vesicular monoamine transporter type 2, which is responsible for importing neurotransmitters from the cytosol to the vesicles in neuronal cells. This transportation contributes to the release of neurotransmitters inside the cell to the synaptic cleft, resulting in dopaminergic signal transmission. The highly potent inhibitory activity of tetrabenazine has led to its advanced applications and in-depth investigation of prodrug design and metabolite drug discovery. In addition, the synthesis of enantiomerically pure tetrabenazine has been pursued. After a series of research studies, tetrabenazine derivatives such as valbenazine and deutetrabenazine have been approved by the US FDA. In addition, radioisotopically labeled tetrabenazine permits the early diagnosis of Parkinson’s disease, which is difficult to treat during the later stages of this disease. These applications were made possible by the synthetic efforts aimed toward the efficient and asymmetric synthesis of tetrabenazine. In this review, various syntheses of tetrabenazine and its derivatives have been summarized.

show abstract

“…[18] Base-mediated excision of the spacer group and directed hydrogenation of the resulting diene provided the complete western (C1-C11) fragment 21 as a single diastereomer with the required configuration at C8. [19] Synthesis of the eastern fragment commenced with asymmetric reduction [20] of ethyl 3-oxohexanoate (22) and protection of the resulting alcohol to give 23 (Scheme 6). Treatment of the ester 23 with an excess of the organocerium reagent prepared from trimethylsilylmethylmagnesium chloride resulted in double Grignard addition.…”

mentioning

confidence: 99%

“…Treatment of the ester 23 with an excess of the organocerium reagent prepared from trimethylsilylmethylmagnesium chloride resulted in double Grignard addition. [21,22] Base-mediated Peterson elimination of the intermediate tertiary alcohol delivered an allylic silane, which was then converted into the bromide 24 by treatment with pyrrolidone hydrotribromide (PHT). [23] Deprotonation of N-propionyloxazolidinone (25) with NaHMDS and enolate alkylation with bromide 24 followed by reductive cleavage of the oxazolidinone auxiliary provided alcohol 26.…”

mentioning

confidence: 99%

Total Syntheses of Amphidinolides T1, T3, and T4

Clark

Romiti

2013

Angew Chem Int Ed

View full text Add to dashboard Cite

Concise and high-yielding total syntheses of amphidinolides T1, T3, and T4 have been completed using an alkynyl macrolactone as a common late-stage intermediate. The required α-hydroxy ketone motif was installed by sequential alkyne hydrosilylation, epoxidation, and Fleming-Tamao oxidation. An oxonium ylide rearrangement formed the trisubstituted tetrahydrofuran core found in the natural products.

show abstract

The cerium (III) mediated reaction of trimethylsilylmethyl magnesium chloride with esters and lactones: The efficient synthesis of some functionalised allylsilanes of use in annulation reactions

Cited by 66 publications

References 12 publications

Synthetic Access to the Mandelalide Family of Macrolides: Development of an Anion Relay Chemistry Strategy

Synthetic Access to the Mandelalide Family of Macrolides: Development of an Anion Relay Chemistry Strategy

Synthesis of Tetrabenazine and Its Derivatives, Pursuing Efficiency and Selectivity

Total Syntheses of Amphidinolides T1, T3, and T4

Contact Info

Product

Resources

About