Enantioselective Intramolecular Oxidative Aminocarbonylation of Alkenylureas Catalyzed by Palladium−Spiro Bis(isoxazoline) Complexes

Tsujihara, Tetsuya; Shinohara, T.; Takenaka, Kazuhiro; Takizawa, Shinobu; Onitsuka, Kiyotaka; Hatanaka, Minoru; Sasai, Hiroaki

doi:10.1021/jo901778a

Cited by 96 publications

(34 citation statements)

References 83 publications

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“…Reaction optimization identified conditions for the cyclization of tosyl urea 169 with increased levels of enantioselectivity. 123 Using cationic Pd(MeCN) 4 (BF 4 ) 2 and the bulkier SPRIX catalyst 149a provided the product in 94% yield and 66% ee. Lowering the ligand loading to a Pd:ligand ratio of 1.1:1 allowed the reaction to be performed at −40 °C, which resulted in an increase to 88% ee, although the reaction required 7 days to reach completion.…”

Section: Enantioselective Reactions Involving Aminopalladationmentioning

confidence: 99%

Palladium(II)-Catalyzed Alkene Functionalization via Nucleopalladation: Stereochemical Pathways and Enantioselective Catalytic Applications

2011

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Section: Enantioselective Reactions Involving Aminopalladationmentioning

confidence: 99%

Palladium(II)-Catalyzed Alkene Functionalization via Nucleopalladation: Stereochemical Pathways and Enantioselective Catalytic Applications

2011

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“…251 The carbon−carbon double bond of suitable substituted N-alkenylureas reacted intramolecularly with one of the nitrogen atoms in the presence of a palladium catalyst under a carbon monoxide atmosphere (Scheme 81). Notably, the use of a chiral spiro bis(isoxazoline) ligand (SPRIX) was essential to obtain the desired products in optically active forms.…”

Section: Palladium-catalyzed Carbonylative Synthesis Of Six-membered mentioning

confidence: 99%

Synthesis of Heterocycles via Palladium-Catalyzed Carbonylations

2012

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Besides the mentioned processes, palladium-catalyzed carbonylation of alkynols represents another powerful methodology for the preparation of lactones. As early as in 1994, Gabriele and co-workers presented a PdI 2 /KI-catalyzed oxidative carbonylation of α-substituted hydroxyalkynes to four-membered lactones in good yields under mild conditions. Later on, they extended this methodology to but-3-yn-1-ols for the synthesis of five-membered lactones (Scheme 4a). 13 Scheme 1. Selected Examples of Heterocyclic Drugs Scheme 2. Palladium-Catalyzed Carbonylative Synthesis of Lactones Scheme 3. Palladium-Catalyzed Carbonylative Synthesis of Lactones from Alkenyloxiranes Scheme 4. Palladium-Catalyzed Carbonylative Synthesis of Lactones from Alkynols Chemical Reviews Review dx.

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“…The use of a chiral spiro bis(isoxazoline) ligand (SPRIX) is essential to realize this reaction in an optically active form. Compared with other ligands, the low σ-donor ability of the isoxazoline coordination site and rigidity of the spiro skeleton make SPRIX the most suitable ligand for this reaction [93]. …”

Section: Scheme 23 Synthesis Of Oxazolines Via Oxidative Carbonylatiomentioning

confidence: 99%

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

Xing

2015

Topics in Heterocyclic Chemistry

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With the assistance of a proper oxidant, carbonylation of two nucleophiles can take place directly in carbonylation conditions, which is defined as oxidative carbonylation. This process starts with the reaction of nucleophiles with the metal catalyst in oxidation state (M (n + 2) ), followed by insertion of CO and subsequent reductive elimination, providing the carbonylated products and the metal catalyst in reduction state (M (n) ). The oxidant could reoxidize M (n) to M (n + 2) to promote the catalytic cycle. Oxidative carbonylation avoids the difficult oxidative addition of R-X to metal catalyst, so this kind of carbonylation could proceed in mild conditions. What's more is that oxidative carbonylation doesn't need prefunctionalization of substrates. So, it's no wonder that considerable attention has been drawn to construct important carbonylated compounds through oxidative carbonylation. Particularly, much progress in synthesis of carbonylated heterocycles via oxidative carbonylation has been achieved in the past decades. Here, we summarized the main achievements in this area from 1982 to the beginning of 2015.

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Enantioselective Intramolecular Oxidative Aminocarbonylation of Alkenylureas Catalyzed by Palladium−Spiro Bis(isoxazoline) Complexes

Cited by 96 publications

References 83 publications

Palladium(II)-Catalyzed Alkene Functionalization via Nucleopalladation: Stereochemical Pathways and Enantioselective Catalytic Applications

Palladium(II)-Catalyzed Alkene Functionalization via Nucleopalladation: Stereochemical Pathways and Enantioselective Catalytic Applications

Synthesis of Heterocycles via Palladium-Catalyzed Carbonylations

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

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