Trifluoroborane catalyzed chemoselective synthesis of highly functionalized 1,3‐thiazin‐2‐ylidenes

Luo, Zhibin; Bhavanarushi, Sangepu; Avula, Sreenivas; Reddy, Narra Srikanth; Valeru, Anil; Khan, Imran; Xu, Yin; Liu, Bin; Xie, Jimin

doi:10.1002/jhet.4049

Cited by 4 publications

(3 citation statements)

References 42 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…First, the reduction of the diketone in the corresponding diol is performed. Several reductants have been used to achieve this reaction (dithionite in a THF/water mixture, − sodium in DMF, or hydrazine sulfate in water). Save the latter case, the diol is usually not isolated and reacted directly as nucleophile with alkyl halides or tosylates in the presence of a base (Cs 2 CO 3 or KOH) to yield the target O-alkylated compound (Scheme ).…”

Section: Divergent Polyfunctionalizationmentioning

confidence: 99%

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Queffélec,

Pati,

Pellegrin

2024

Chem. Rev.

View full text Add to dashboard Cite

1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range of metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading to intriguing features in numerous fields (luminescent coordination scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions for functional groups to be attached, showcasing remarkable versatility for such a simple ligand. As a result, phen has become a landmark molecule for coordination chemists, serving as a must-use ligand and a versatile platform for designing polyfunctional arrays. The extensive use of substituted phenanthroline ligands with different metal ions has resulted in a diverse array of complexes tailored for numerous applications. For instance, these complexes have been utilized as sensitizers in dye-sensitized solar cells, as luminescent probes modified with antibodies for biomaterials, and in the creation of elegant supramolecular architectures like rotaxanes and catenanes, exemplified by Sauvage’s Nobel Prize-winning work in 2016. In summary, phen has found applications in almost every facet of chemistry. An intriguing aspect of phen is the specific reactivity of each pair of carbon atoms ([2,9], [3,8], [4,7], and [5,6]), enabling the functionalization of each pair with different groups and leading to polyfunctional arrays. Furthermore, it is possible to differentiate each position in these pairs, resulting in non-symmetrical systems with tremendous versatility. In this Review, the authors aim to compile and categorize existing synthetic strategies for the stepwise polyfunctionalization of phen in various positions. This comprehensive toolbox will aid coordination chemists in designing virtually any polyfunctional ligand. The survey will encompass seminal work from the 1950s to the present day. The scope of the Review will be limited to 1,10-phenanthroline, excluding ligands with more intracyclic heteroatoms or fused aromatic cycles. Overall, the primary goal of this Review is to highlight both old and recent synthetic strategies that find applicability in the mentioned applications. By doing so, the authors hope to establish a first reference for phenanthroline synthesis, covering all possible positions on the backbone, and hope to inspire all concerned chemists to devise new strategies that have not yet been explored.

show abstract

Section: Divergent Polyfunctionalizationmentioning

confidence: 99%

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Queffélec,

Pati,

Pellegrin

2024

Chem. Rev.

View full text Add to dashboard Cite

show abstract

“…A Lewis acid catalysis system was used in Luo′s work for the treatment of β‐aroyl‐thioacetamide 125 with propargylic alcohols 1 to achieve 1,3‐thiazine‐2‐ylidenes 126 as desired products (Scheme 51). [52] The reaction proceeded through the chelation of BF 3 .OEt 2 with OH group of propargyl alcohols 1 to simplify both leaving of OH and attack of sulfur in compound 125 to generate intermediate A , followed by intramolecular N‐cyclization to afford product 126 . Evaluating several Lewis acids, including P 2 O 5 , Zn(OTf) 2 , ZnCl 2 , InCl 3 , AlCl 3 , and also Brønsted acid p ‐TSA, resulted in inferior chemical yields.…”

Section: Propargylic Alcohols In Cyclization Reactionsmentioning

confidence: 99%

Recent Progress in Application of Propargylic Alcohols in Organic Syntheses

Doraghi,

Mohammad Mahdavian,

Karimian

et al. 2023

Adv Synth Catal

View full text Add to dashboard Cite

Propargylic alcohols are readily available bifunctional (alkyne and hydroxyl groups) synthons, which recognize as one of the attractive synthetic feedstock in organic transformations. Especially, in recent years the employment of these valuable molecules has frequently been observed in the literature. Hence, the present review highlights recent advancements in the application of propargylic alcohols in the cyclization, substitution, and addition reactions.

show abstract

“…Some molecules containing thiazine moiety have also shown potential antifungal or antibacterial activities in the field of pesticides [ 9 , 10 , 11 ]. Therefore, the development of quick and efficient strategies to construct thiazine scaffolds from readily available chemicals is of particular interest and has certainly attracted considerable attention in organic synthesis [ 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. On the other hand, axial chirality is a common phenomenon in modern organic synthesis and living systems.…”

Section: Introductionmentioning

confidence: 99%

Carbene-Catalyzed Atroposelective Annulation for Quick Access to Axially Chiral Thiazine Derivatives

Yang

Chen

et al. 2023

Molecules

View full text Add to dashboard Cite

An N-heterocyclic carbene (NHC)-catalyzed atroposelective annulation reaction is disclosed for quick and efficient access to thiazine derivatives. A series of axially chiral thiazine derivatives bearing various substituents and substitution patterns were produced in moderate to high yields with moderate to excellent optical purities. Preliminary studies revealed that some of our products exhibit promising antibacterial activities against Xanthomonas oryzae pv. oryzae (Xoo) that causes rice bacterial blight.

show abstract

Trifluoroborane catalyzed chemoselective synthesis of highly functionalized 1,3‐thiazin‐2‐ylidenes

Cited by 4 publications

References 42 publications

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Recent Progress in Application of Propargylic Alcohols in Organic Syntheses

Carbene-Catalyzed Atroposelective Annulation for Quick Access to Axially Chiral Thiazine Derivatives

Contact Info

Product

Resources

About