KHMDS Enhanced SmI<sub>2</sub>-Mediated Reformatsky Type α-Cyanation

Ankner, Tobias; Fridén-Saxin, Maria; Pemberton, Nils; Seifert, Tina; Grøtli, Morten; Luthman, Kristina; Hilmersson, Göran

doi:10.1021/ol100424y

Cited by 41 publications

(19 citation statements)

References 54 publications

(23 reference statements)

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Ü Ü a functionalization of biologically significant chromanones under mild reaction conditions (Scheme 20). [50] A variety of alkyl and aryl chromanones underwent a cyanation in excellent yields. However, the sensitive nature of these products prevented their efficient isolation.…”

Section: Samarium(ii) Amidesmentioning

confidence: 99%

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

2012

View full text Add to dashboard Cite

Reactions proceeding through open-shell, single-electron pathways offer attractive alternative outcomes to those proceeding through closed-shell, two-electron mechanisms. In this context, samarium diiodide (SmI(2)) has emerged as one of the most important and convenient-to-use electron-transfer reagents available in the laboratory. Recently, significant progress has been made in the reductive chemistry of other divalent lanthanides which for many years had been considered too reactive to be of value to synthetic chemists. Herein, we illustrate how new samarium(II) complexes and nonclassical lanthanide(II) reagents are changing the landscape of modern reductive chemistry.

show abstract

Section: Samarium(ii) Amidesmentioning

confidence: 99%

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

2012

View full text Add to dashboard Cite

show abstract

“…28 The incorporation of various functional groups to furnish highly substituted structures have successfully been conducted through different Pd-mediated cross-coupling reactions, 29,30 through Mannich reactions, 31 and via a SmI 2 –KHMDS-mediated Reformatsky type reaction. 32 Recently, we have also developed chromone/chroman-4-one-based β-turn peptidomimetics. 31,33 In the present study we report substituted chromone and chroman-4-one derivatives as potent and highly selective SIRT2 inhibitors.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Evaluation of Substituted Chroman-4-one and Chromone Derivatives as Sirtuin 2-Selective Inhibitors

et al. 2012

Self Cite

View full text Add to dashboard Cite

A series of substituted chromone/chroman-4-one derivatives has been synthesized and evaluated as novel inhibitors of SIRT2, an enzyme involved in aging-related diseases, e.g., neurodegenerative disorders. The analogues were efficiently synthesized in a one-step procedure including a base-mediated aldol condensation using microwave irradiation. The most potent compounds, with inhibitory concentrations in the low micromolar range, were substituted in the 2-, 6-, and 8-positions. Larger, electron-withdrawing substituents in the 6- and 8-positions were favorable. The most potent inhibitor of SIRT2 was 6,8-dibromo-2-pentylchroman-4-one with an IC50 of 1.5 μM. The synthesized compounds show high selectivity toward SIRT2 over SIRT1 and SIRT3 and represent an important starting point for the development of novel SIRT2 inhibitors.

show abstract

“…Reformatsky-type electrophilic cyanation reactions, which permit a cyano group to be introduced into the α-position of a chroman-4-one skeleton were reported by Hilmersson and co-workers. 34 The target compounds were difficult to access by other electrophilic approaches, due to the high sensitivity of the chroman-4-ones. By employing a reductive method using SmI 2 (2.2 equiv) and potassium hexamethyldisilazanide (KHMDS) (2.2 equiv), 3-bromochroman-4-ones effectively underwent cyanation with TsCN in THF at -78 °C (Scheme 18).…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Recent Advances in the Synthesis of β-Ketonitriles

2017

View full text Add to dashboard Cite

β-Ketonitriles are an important class of compounds in the field of organic and medicinal chemistry. Over the past decades, numerous efforts have been devoted to the development of new and efficient methodologies for the synthesis of these derivatives, and a number of efficient methods to accomplish this have been developed in recent years. In this context, this short review highlights recent advances in the synthesis of β-ketonitriles.1 Introduction2 Acylation of Alkyl Nitriles3 Electrophilic Cyanation of Ketone Enolates4 Electrophilic Cyanation of β-Keto Carbonyl Compounds5 Transition-Metal-Catalyzed Carbonylative Coupling Reactions6 Miscellaneous Examples7 Outlook

show abstract

KHMDS Enhanced SmI₂-Mediated Reformatsky Type α-Cyanation

Cited by 41 publications

References 54 publications

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Synthesis and Evaluation of Substituted Chroman-4-one and Chromone Derivatives as Sirtuin 2-Selective Inhibitors

Recent Advances in the Synthesis of β-Ketonitriles

Contact Info

Product

Resources

About

KHMDS Enhanced SmI2-Mediated Reformatsky Type α-Cyanation

Cited by 41 publications

References 54 publications

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Beyond Samarium Diiodide: Vistas in Reductive Chemistry Mediated by Lanthanides(II)

Synthesis and Evaluation of Substituted Chroman-4-one and Chromone Derivatives as Sirtuin 2-Selective Inhibitors

Recent Advances in the Synthesis of β-Ketonitriles

Contact Info

Product

Resources

About

KHMDS Enhanced SmI₂-Mediated Reformatsky Type α-Cyanation