NHC catalyzed enantioselective Coates-Claisen rearrangement: a rapid access to the dihydropyran core for oleuropein based secoiridoids

Vedachalam, Seenuvasan; Murugesh, Nithya; Chakraborty, Priyanka; Karvembu, Ramasamy; Liu, Xuewei

doi:10.1039/c7nj04057a

Cited by 15 publications

(11 citation statements)

References 65 publications

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“…In 2010, Bode and colleagues reported an enantioselective NHC-catalyzed Claisen rearrangement between ynals and enols to produce enantiomerically enriched dihydropyranones [39]. Most recently, in 2018, Vedachalam and co-workers reported a NHC-catalyzed Coates-Claisen rearrangement to construct the dihydropyran core of secoiridoids (Scheme 14a) [40]. Although traditional imidazolinium-based NHCs with both aliphatic chains and aromatic groups are not reactive in the Coates-Claisen rearrangement, the use of the fused NHC 66 afforded the corresponding compound dihydropyran-based lactone 65 in 62% yield and 82% ee.…”

Section: Organocatalyzed Claisen Rearrangementmentioning

confidence: 99%

Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

Lee

Kim

et al. 2022

Catalysts

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Carbon–carbon bond formation by [3,3]-sigmatropic rearrangement is a fundamental and powerful method that has been used to build organic molecules for a long time. Initially, Claisen and Cope rearrangements proceeded at high temperatures with limited scopes. By introducing catalytic systems, highly functionalized substrates have become accessible for forming complex structures under mild conditions, and asymmetric synthesis can be achieved by using chiral catalytic systems. This review describes recent breakthroughs in catalytic [3,3]-sigmatropic rearrangements since 2016. Detailed reaction mechanisms are discussed to enable an understanding of the reactivity and selectivity of the reactions. Finally, this review is inspires the development of new cascade reaction pathways employing catalytic [3,3]-sigmatropic rearrangement as related methodologies for the synthesis of complex functional molecules.

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Section: Organocatalyzed Claisen Rearrangementmentioning

confidence: 99%

Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

Lee

Kim

et al. 2022

Catalysts

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“…. 15 To a solution of 2.8 g (40 mmol) of 3-butyn-1-ol in 200 mL of CH2Cl2 were added 5.8 g (80 mmol) of imidazole and 9.68 g (60 mmol) of t-butyldimethylsilyl chloride and the solution was stirred under argon at 25 o C for 12 h. The resulting solution was washed twice with water (50 mL each) and brine (50 mL), dried (anhydrous Na2SO4), concentrated, and column chromatographed on silica gel using a mixture of hexane and EtOAc (5:1) as an eluent to obtain 6.90 g (97% yield) of the title compound as a colorless oil; 1 H NMR 15 (400 MHz, CDCl3)…”

Section: -(Tert-butyldimethylsilyloxy)-1-butyne (14)mentioning

confidence: 99%

Synthesis of Probe Molecules, 6-(Dimethylamino)-2-phenylisoindolin-1-ones, for Mechanistic Studies of Firefly Luciferase Inhibition

Hua¹,

Gunaratna²,

Hao³

et al. 2021

HETEROCYCLES

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Firefly luciferase is used in high-throughput screening based on the detection of chemiluminescence. It catalyzes an esterification reaction of luciferin with adenosine 5'-triphosphate (ATP) followed by decarbonylation with oxygen and concomitance of light. Previously, we reported that firefly luciferase also possesses acyl-CoA synthetase activity and catalyzes an aromatic carboxylic acid group of F-53, using ATP, Mg 2+ and coenzyme A (CoA), to produce F-53 covalently attached to active-site lysine-529 residue of firefly luciferase through the formation of an amide group. The amidation of lysine-529 resulted in a deactivation of luciferase. In order to probe firefly luciferase inhibition's mechanism, we synthesized two probe molecules 1 and 2, mimicking F-53.Molecule 1 contains an azido-appended side chain in the aromatic ring of F-53, while 2 possesses an azido and a carboxylic acid group appended side chains.Both synthetic schemes are readily amenable to large-scale syntheses. Molecule 1 was made from 2-allylaniline, which was derived from a thermal-induced aromatic-Claisen rearrangement of N-allylaniline. The azido-appended side chain of 2 was installed from a Horner-Wadsworth-Emmons reaction and the carboxylic acid side chain from a Sonogashira reaction.

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“…Furthermore, an additional advantage is the example of use in total synthesis. Liu and co-workers used the Coates-Claisen reaction in the synthesis of a dihydropyran core for oleuropein based secoiridoids (Scheme 9) [112].…”

Section: Scheme 2 Breslow Intermediatementioning

confidence: 99%

Organocatalytic Name Reactions Enabled by NHCs

et al. 2020

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Giving reactions the names of their discoverers is an extraordinary tradition of organic chemistry. Nowadays, this phenomenon is much rarer, although already named historical reactions are still often developed. This is also true in the case of a broad branch of N‑heterocyclic carbenes catalysis. NHCs allow many unique synthetic paths, including commonly known name reactions. This article aims to gather this extensive knowledge and compare historical reactions with current developed processes. Furthermore, this review is a great opportunity to highlight some of the unique applications of these procedures in the total synthesis of biologically active compounds. Hence, this concise article may also be a source of knowledge for scientists just starting their adventure with N‑heterocyclic carbene chemistry.

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NHC catalyzed enantioselective Coates-Claisen rearrangement: a rapid access to the dihydropyran core for oleuropein based secoiridoids

Abstract: A simple protocol for the synthesis of the dihydropyran core structure of secoiridoids using NHC catalyzed Coates-Claisen rearrangement is described.

Cited by 15 publications

References 65 publications

Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

Recent Advances in Catalytic [3,3]-Sigmatropic Rearrangements

Synthesis of Probe Molecules, 6-(Dimethylamino)-2-phenylisoindolin-1-ones, for Mechanistic Studies of Firefly Luciferase Inhibition

Organocatalytic Name Reactions Enabled by NHCs

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