Deacylation of Esters, Thioesters and Amides by a Naphthalene-Catalysed Lithiation

Behloul, Cherif; Guijarro, David; Yus, Miguel

doi:10.1055/s-2005-918501

Synthesis

2006

DOI: 10.1055/s-2005-918501

|View full text |Cite

Deacylation of Esters, Thioesters and Amides by a Naphthalene-Catalysed Lithiation

Cherif Behloul¹,

David Guijarro²,

Miguel Yus³

Abstract: The reaction of different esters, thioesters and amides derived from pivalic, benzoic and 4-tert-butylbenzoic acids with an excess of lithium and a catalytic amount of naphthalene (8 mol%) led, after methanolysis, to the corresponding alcohols, thiols and amines, respectively, through a reductive non-hydrolytic procedure. This methodology represents a reasonable alternative to other nonreductive protocols.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2016

2021

Publication Types

Select...

Article3

Relationship

Self Cite0

Independent3

Authors

Journals

Cited by 3 publications

References 7 publications

(12 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives

et al. 2021

View full text Add to dashboard Cite

Insight into the mechanism of a safe, simple, and inexpensive phosphoric acid (H3PO4)-catalyzed acylation of alcohols with acid anhydrides is described. The corresponding in situ-generated diacylated mixed anhydrides, unlike traditionally proposed monoacylated mixed anhydrides, are proposed as the active species. In particular, the diacylated mixed anhydrides act as efficient catalytic acyl transfer reagents rather than as Brønsted acid catalysts simply activating acid anhydrides. Remarkably, highly efficient phosphoric acid (1–3 mol %)-catalyzed acylation of alcohols with acid anhydrides was achieved and a 23 g scale synthesis of an ester was demonstrated. Also, phosphoric acid catalyst was effective for synthetically useful esterification from carboxylic acids, alcohols, and acid anhydride. Moreover, with regard to recent developments in chiral 1,1′-bi-2-naphthol (BINOL)-derived phosphoric acid diester catalysts toward asymmetric kinetic resolution of alcohols by acylation, some phosphate diesters were examined. As a result, a 31P NMR study and a kinetics study strongly supported not only the acid–base cooperative mechanism as previously proposed by other researchers but also the mixed anhydride mechanism as presently proposed by us.

show abstract

Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives

et al. 2021

View full text Add to dashboard Cite

show abstract

Pd/C-Catalyzed Aminocarbonylation of Aryl Iodides via Oxidative C–N Bond Activation of Tertiary Amines to Tertiary Amides

Mane

Bhanage

2016

J. Org. Chem.

View full text Add to dashboard Cite

show abstract

Amine-Functionalized Nanoporous Silica Monoliths for Heterogeneous Catalysis of the Knoevenagel Condensation in Flow

et al. 2020

View full text Add to dashboard Cite

Porous carrier materials functionalized with organocatalysts offer substantial advantages compared to homogeneous catalysts, e.g., easy separation of the catalyst, scalability, and an improved implementation in continuous operations. Here, we report the immobilization of (3-aminopropyl)trimethoxysilane (APTMS) onto self-prepared silica monoliths and its application as a heterogeneous catalyst in the Knoevenagel condensation between cyano ethylacetate and various aromatic aldehydes under continuous-flow conditions. The meso-macroporous silica monoliths (6−7 cm in length) were optimized to be used in flow taking advantage of their hierarchical meso-and macroporosity. The monoliths were cladded with a poly(ether ether ketone) (PEEK) tube by a refined procedure to guarantee tight connection between the carrier material and PEEK. Functionalization of the bare silica monoliths consisting of APTMS can be efficiently performed in flow in ethanol and toluene. While a large grafting gradient is obtained for toluene, the grafting in ethanol proceeds homogenously throughout the monolith, as evidenced by elemental analysis and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The silica monoliths exhibit high conversion up to 95% with concurrent low back pressures, which is of importance in flow catalysis. By connecting two monoliths, high conversions can be maintained for several flow rates. Two types of monoliths were synthesized, possessing different mesopore sizes. The monolith bearing the larger mesopore size showed an enhanced turnover frequency (TOF), while the monolith with the smaller mesopores allowed for larger quantities of the product to be synthesized, due to the higher surface area. A long-term stability test showed that the functionalized monoliths were still active after 66 h of continuous usage, while the overall yield decreased over time.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Deacylation of Esters, Thioesters and Amides by a Naphthalene-Catalysed Lithiation

Cited by 3 publications

References 7 publications

Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives

Insight into the Mechanism of the Acylation of Alcohols with Acid Anhydrides Catalyzed by Phosphoric Acid Derivatives

Pd/C-Catalyzed Aminocarbonylation of Aryl Iodides via Oxidative C–N Bond Activation of Tertiary Amines to Tertiary Amides

Amine-Functionalized Nanoporous Silica Monoliths for Heterogeneous Catalysis of the Knoevenagel Condensation in Flow

Contact Info

Product

Resources

About