Enantioselective Wacker-Type Cyclization of 2-Alkenyl-1,3-diketones Promoted by Pd-SPRIX Catalyst

Takenaka, Kazuhiro; Mohanta, Suman C.; Patil, Mahesh L.; Rao, Changqing; Takizawa, Shinobu; Suzuki, Takayoshi; Sasai, Hiroaki

doi:10.1021/ol1013069

Cited by 46 publications

(18 citation statements)

References 25 publications

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“…Cyclopentanone (0.846 g, 10.1 mmol), methyl iodide (5.0 mL, 80.3 mmol) and potassium hydroxide (11,2 g, 200 mmol) were added and the mixture was stirred magnetically for 1h.T he mixture was cooled to 0 8C and extracted with pentane (3 7mL). 1 HNMR (300 MHz, CDCl 3 ): [49] Synthesis of 3,6,6-trimethylcyclohex-2-en-1-one (16): [50] 3,6,6-Trimethylcyclohex-2-en-1-one (16)w as synthesized in two steps. The colorless oil obtained as crude reaction product consisted of pure 2,2,5,5-tetramethylcyclopentanone (2,0 .879 g, 6.28 mmol, 62 %y ield).…”

Section: Methodsmentioning

confidence: 99%

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

Oliver-Tomas

Renz

Corma

2017

Chemistry A European J

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For the reaction mechanism of the ketonic decarboxylation of two carboxylic acids, a β-keto acid is favored as key intermediate in many experimental and theoretical studies. Hydrogen atoms in the α-position are an indispensable requirement for the substrates to react by following this mechanism. However, isolated observations with tertiary carboxylic acids are not consistent with it and these are revisited and discussed herein. The experimental results obtained with pivalic acid indicate that the ketonic decarboxylation does not occur with this substrate. Instead, it is consumed in alternative reactions such as disintegration into isobutene, carbon monoxide, and water (retro-Koch reaction). In addition, the carboxylic acid is isomerized or loses carbon atoms, which converts the tertiary carboxylic acid into carboxylic acids bearing α-proton atoms. Hence, the latter are suitable to react through the β-keto acid pathway. A second substrate, 2,2,5,5-tetramethyladipic acid, reacted by following the same retro-Koch pathway. The primary product was the monocarboxylic acid 2,2,5-trimethyl-4-hexenoic acid (and its double bond isomer), which might be further transformed into a cyclic enone or a lactone. The ketonic decarboxylation product, 2,2,5,5-tetramethylcyclopentanone was observed in traces (<0.2 % yield). Therefore, it can be concluded that the observed experimental results further support the proposed mechanism for the ketonic decarboxylation via the β-keto acid intermediate.

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Section: Methodsmentioning

confidence: 99%

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

Oliver-Tomas

Renz

Corma

2017

Chemistry A European J

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“…( P,R,R )‐ 1 f : [α] D = −115.8 ( c = 0.82, CHCl 3 ). ( M,S,S )‐ 1f : [α] D = +119.4 ( c = 0.13, CHCl 3 ).…”

Section: Methodsmentioning

confidence: 99%

Structural Features and Asymmetric Environment of i‐Pr‐SPRIX Ligand

et al. 2015

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Novel chiral diisopropyl spiro bis(isoxazoline) ligands, anti-i-Pr-SPRIX and syn-i-Pr-SPRIX, were designed and synthesized. Their catalytic utility, X-ray crystallographic analyses, and complexation studies demonstrated the structural features of tetraisopropyl spiro bis(isoxazoline) ligand, i-Pr-SPRIX, which is a prominent ligand in various enantioselective Pd catalytic processes: All i-Pr groups work in collaboration to create an effective asymmetric environment.

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“…93,94 Such nucleophiles, which can readily form an enol structure, cyclized in the presence of a Pd(TFA) 2 /SPRIX 149a catalyst to furnish 6- endo - trig products (Scheme 56). The SPRIX ligand appears to be uniquely successful in this reaction.…”

Section: Enantioselective Reactions Involving Oxypalladationmentioning

confidence: 99%

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

2011

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Enantioselective Wacker-Type Cyclization of 2-Alkenyl-1,3-diketones Promoted by Pd-SPRIX Catalyst

Cited by 46 publications

References 25 publications

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

Ketone Formation from Carboxylic Acids by Ketonic Decarboxylation: The Exceptional Case of the Tertiary Carboxylic Acids

Structural Features and Asymmetric Environment of i‐Pr‐SPRIX Ligand

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

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