Reactivity of β-Lactamido <i>N</i>-Sulfonyl Radicals

Montermini, Florian; Lacôte, Emmanuel; Malacrìa, Max

doi:10.1021/ol0363725

Cited by 19 publications

(9 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…3,3-Dibromosubstituted b-lactams can be dehalogenated or C3-functionalizated by treatment with methyl acrylate under radical conditions [126]. Upon using triethylborane as the radical initiator, b-lactamido N-sulfonyl radicals could be allylated and added onto electron-rich olefins [127]. The radicals do not undergo desulfonylation and are electrophilic in nature.…”

Section: Radical Transformationsmentioning

confidence: 99%

The Chemistry of 2‐Azetidinones (β‐Lactams)

Alcaide¹,

Almendros²,

Luna³

2011

Modern Heterocyclic Chemistry

View full text Add to dashboard Cite

The large number of recent reports on b-lactam chemistry demonstrates the increasing interest in this important class of compounds. Monocyclic b-lactams frequently serve as precursors for the synthesis of classical bicyclic b-lactam antibiotics. The cyclic 2-azetidinone skeleton has been extensively used as a template on which to build the heterocyclic structure fused to the four-membered ring, using the chirality and functionalization of the b-lactam nucleus as a stereocontrolling element. The discovery of nonclassical b-lactam antibiotics, such as monobactams and nocardicins, coupled with ever-growing new applications such as enzyme inhibition has triggered a renewed interest in the building of new monocyclic b-lactam derivatives. Besides the utility of b-lactams as biologically active agents, they are used as intermediates in a-and b-amino acid synthesis, as well as building blocks for alkaloids, heterocycles, taxoids and other types of compounds of biological and medicinal interest. Physicochemical Data Computational ChemistryTheoretical studies show that b-lactams are weaker bases, in the gas phase, than acyclic amides [1]. The attenuation of basicity upon cyclization is stronger than that found for cyclic ketones of similar size due to the existence of a negative hyperconjugation effect that is present in b-lactams but not in cyclic ketones. Ab initio calculations indicate that both b-lactams and acyclic amides are oxygen bases, but the gap between the oxygen and nitrogen intrinsic basicities is much smaller in the former due to the aforementioned cyclization effects. This decrease of the oxygen Modern Heterocyclic Chemistry, First Edition. Edited

show abstract

Section: Radical Transformationsmentioning

confidence: 99%

The Chemistry of 2‐Azetidinones (β‐Lactams)

Alcaide¹,

Almendros²,

Luna³

2011

Modern Heterocyclic Chemistry

View full text Add to dashboard Cite

show abstract

“…Reaction of N-chlorosulfonyl derivatives with enol ether initiated by Et 3 B has been reported (Scheme 22) [57]. The reaction mechanism involves a chlorine atom transfer followed by a Et 3 N promoted elimination of HCl to produce stable enol ethers.…”

Section: Chlorine Atom Transfermentioning

confidence: 99%

Tin-Free Radical Reactions Mediated by Organoboron Compounds

Darmency

Renaud

2006

Radicals in Synthesis I

View full text Add to dashboard Cite

“…4), 25 Lacôte and co-workers performed a radical-mediated coupling of chlorosulfonamides with allyl stannanes (eq. 5), 26 and Arnswald and co-workers utilized aryl stannanes in a Friedel-Crafts-like ipso substitution reaction with chlorosulfonyl isocyanate (eq. 6).…”

mentioning

confidence: 99%

“…Interestingly, to the best of our knowledge, only three examples of this transformation using an S(VI) source are reported in the literature (Figure 2). Nishimura and co-workers opened an N-alkyl thiadiazolidinone 1,1-dioxide with methyl magnesium bromide to form a methanesulfonamide (Figure 2, eq 4), 24 Lacote and co-workers performed a radical-mediated coupling of chlorosulfonamides with allyl stannanes (Figure 2, eq 5), 25 Friedel−Crafts-like ipso substitution reaction with chlorosulfonyl isocyanate (Figure 2, eq 6). 26 This last example is related to a large, but rarely utilized, subset of chemistry using N-carbamoyl sulfamide inner salts.…”

mentioning

confidence: 99%

The Synthesis of Alkyl and (Hetero)aryl Sulfonamides From Sulfamoyl Inner Salts

et al. 2015

View full text Add to dashboard Cite

An approach to the synthesis of sulfonamides from sulfamoyl inner salts and organometallic species is presented. A range of sulfamoyl carbamates, amines, and metals are explored. Primary, secondary, and tertiary alkyl-, aryl-, and heteroaryllitihium and magnesium nucleophiles were successful. This approach yields bench-stable intermediates and avoids many of the functional group incompatibilities, regioselectivity issues, and high-energy reagents generally associated with the synthesis of sulfonamides. Additionally, the products may be purified by basic extraction or salt formation, avoiding chromatography.

show abstract

Reactivity of β-Lactamido N-Sulfonyl Radicals

Cited by 19 publications

References 33 publications

The Chemistry of 2‐Azetidinones (β‐Lactams)

The Chemistry of 2‐Azetidinones (β‐Lactams)

Tin-Free Radical Reactions Mediated by Organoboron Compounds

The Synthesis of Alkyl and (Hetero)aryl Sulfonamides From Sulfamoyl Inner Salts

Contact Info

Product

Resources

About