An Unusual Synthesis of <i>N</i>-Unsubstituted Benzazepinones

Quiclet‐Sire, Béatrice; Tran, Ngoc Diem My; Zard, Samir Z.

doi:10.1021/ol3026044

Cited by 30 publications

(23 citation statements)

References 25 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Examples of a polycyclic azetine and a benzazepinone [42,43]. conjugated with the nitrile group and, therefore, electrophilic and susceptible to conjugate attack by the aniline to give indoline 92.…”

Section: Scheme 16mentioning

confidence: 99%

Some aspects of radical cascade and relay reactions

Quiclet‐Sire¹,

Zard²

2017

Proc. R. Soc. A.

Self Cite

View full text Add to dashboard Cite

The ability to create carbon-carbon bonds is at the heart of organic synthesis. Radical processes are particularly apt at creating such bonds, especially in cascade or relay sequences where more than one bond is formed, allowing for a rapid assembly of complex structures. In the present brief overview, examples taken from the authors' laboratory will serve to illustrate the strategic impact of radical-based approaches on synthetic planning. Transformations involving nitrogen-centred radicals, electron transfer from metallic nickel and the reversible degenerative exchange of xanthates will be presented and discussed. The last method has proved to be a particularly powerful tool for the intermolecular creation of carbon-carbon bonds by radical additions even to unactivated alkenes. Various functional groups can be brought into the same molecule in a convergent manner and made to react together in order to further increase the structural complexity. One important benefit of this chemistry is the so-called RAFT/MADIX technology for the manufacture of block copolymers of almost any desired architecture.

show abstract

Section: Scheme 16mentioning

confidence: 99%

Some aspects of radical cascade and relay reactions

Quiclet‐Sire¹,

Zard²

2017

Proc. R. Soc. A.

Self Cite

View full text Add to dashboard Cite

show abstract

“…73,[75][76][77] Additionally, examples of silyl ethers, 78 hydroxamate esters, 79 amides, [80][81][82] and ethers 83,84 have been reported. There is also a series of isolated reports of aryl migrations to carbon believed to proceed by photochemical processes.…”

Section: Radical Mechanismsmentioning

confidence: 99%

The Truce–Smiles rearrangement and related reactions: a review

2017

View full text Add to dashboard Cite

Abstract:The Truce-Smiles rearrangement is an X ¡ C aryl migration reaction that is achieved by an intramolecular nucleophilic aromatic substitution pathway. The reaction exhibits a wide substrate scope with respect to a migrating aryl ring and leaving group, appearing in many different tandem reaction sequences, to achieve a wide variety of product outcomes. We present an extensive survey of reported examples of the Truce-Smiles rearrangement from the chemistry literature (1950s until present) organized by various substrate design variables or aspects of the reaction method. Present deficiencies in our understanding of the reaction are identified with recommendations for future research directions and useful developments in the application of the reaction are celebrated.

show abstract

“…While the same applies to fused seven-membered rings, it is nevertheless possible to access N-unsubstituted benzazepinones by starting with N-acetoxy-anilide derivatives such as compound 37, itself made by radical addition of xanthate 35 to allylboronate 36. 18 The The examples in Scheme 6 involve a permanent fusion of a 5-, 6-, or 7-membered ring onto an aromatic platform. It is also possible to exploit the temporary formation of a spirocyclic intermediate that results in ultimately the shifting of the aromatic ring along the carbon backbone.…”

Section: Scheme 5 Synthesis Of Complex Fluoro-olefinsmentioning

confidence: 99%

“…67, X = SCSOC18 H 37 68, X = H H 3 PO 2 , Et 3 N, (AIBN) Please do not adjust margins formation of indolines 72 and the second for the aromatisation into indoles 74) Scheme 16 Syntheses of difluoroethyl-(aza)indoles.Access to 1,1-difluoro-1,3-dienes can be secured by reacting xanthate 65c with the allylic fluoropyridoxy reagents discussed above (c. f. Schemes 3, 4, and 5) followed by base induced elimination of HCl 30. Thus, addition-fragmentation to genericsubstrate 75 furnishes alkene 76 and thence diene 77 (Scheme 17).…”

mentioning

confidence: 99%

The xanthate route to organofluorine derivatives. A brief account

Zard

2016

Org. Biomol. Chem.

Self Cite

View full text Add to dashboard Cite

The present account summarises routes to organofluorine derivatives based on the chemistry of xanthates developed in the author's laboratory. It concerns mostly radical pathways, but a few ionic transformations are also discussed. The degenerative reversible transfer of xanthates allows radical addition even to unactivated alkenes and tolerates numerous functional groups, in particular common polar groups such as ketones, esters, amides, carbamates, nitriles etc. Since the fluorine atoms can be placed on the alkene or the xanthate partner or on both, this opens a convergent approach to a vast array of otherwise inaccessible organofluorine structures that could be of interest to the pharmaceutical and agrochemical industries and to materials science.

show abstract

An Unusual Synthesis of N-Unsubstituted Benzazepinones

Abstract: A short route to novel bicyclic N-unprotected benzazepinones is described starting from N-acetoxyanilides involving radical addition and cyclization with concomitant homolytic rupture of the N-O bond.

Cited by 30 publications

References 25 publications

Some aspects of radical cascade and relay reactions

Some aspects of radical cascade and relay reactions

The Truce–Smiles rearrangement and related reactions: a review

The xanthate route to organofluorine derivatives. A brief account

Contact Info

Product

Resources

About