Palladium‐Catalyzed Enantioselective Intramolecular Hydroarylation of Alkynes To Form Axially Chiral 4‐Aryl 2‐Quinolinones

Shibuya, Tetsuro; Shibata, Yu; Noguchi, Keiichi; Tanaka, Ken

doi:10.1002/ange.201100152

Cited by 17 publications

(1 citation statement)

References 66 publications

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“…Our research group recently reported the enantioselective intramolecular 6‐ endo hydroarylation of N ‐arylpropiolamides, which was catalyzed by palladium(II)/xyl‐H 8 ‐binap (xyl‐H 8 ‐binap=2,2′‐bis[di(3,5‐xylyl)phosphine]‐5,5′,6,6′,7,7′,8,8′‐octahydro‐1,1′‐binaphthyl). This system furnishes axially chiral 4‐aryl‐2‐quinolinones with good yields and ee values 9–11. In this reaction, N ‐(2‐naphthyl)propiolamides showed high reactivity.…”

Section: Methodsmentioning

confidence: 99%

Dearomatization of Fused Arenes Using Platinum‐Catalyzed Intramolecular Formation of Two CC Bonds

2012

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Section: Methodsmentioning

confidence: 99%

Dearomatization of Fused Arenes Using Platinum‐Catalyzed Intramolecular Formation of Two CC Bonds

2012

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Palladium‐Catalyzed CS Activation/Aryne Insertion/Coupling Sequence: Synthesis of Functionalized 2‐Quinolinones

et al. 2014

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Abstract:The insertion of an aryne into a C À S bond can suppress the addition of an S nucleophile to the aryne in the presence of palladium. Catalyzed by Pd(OAc) 2 , a wide range of a-carbamoyl ketene dithioacetals readily react with arynes to selectively afford functionalized 2-quinolinones in high yields under neutral reaction conditions by a C À S activation/ aryne insertion/intramolecular coupling sequence. The attractive feature of the new strategy also lies in the versatile transformations of the alkythio-substituted quinolinone products. Transition-metal-catalyzedCÀSbondactivationforCÀCandC-heteroatom bond formation has fascinated organic chemists for decades.[1] A variety of organosulfur compounds have been utilized and have great potential in these processes [1][2][3] because of their ready availability, stability, and structural diversity, as compared to the corresponding organic halide coupling partners.[4] Cross-coupling chemistry with thioorganics along with new reaction patterns, exceptional selectivity, or unique reactivity would be highly desirable.Inspired by palladium-catalyzed desulfitative coupling of thioesters, [1c, 2a-d] we recently became interested in transitionmetal-catalyzed CÀS bond cleavage for CÀC bond formation during our research [5] on ketene dithioacetals, which are easily prepared and widely applied as organic intermediates.[6] We have already achieved copper-catalyzed desulfitative C À C cross-coupling of a-oxo ketene dithioacetals with arylboronic acids, [3a] and then palladium-catalyzed/copper-mediated desulfitative annulation of 2-methylthiobenzofurans with 2-hydroxyphenylboronic acids.[3b] More recently, a CÀS bond activation protocol for Heck-type cyclization of a-alkenoyl ketene dithioacetals was also developed in our group.[3c] To take advantage of the synthetic power of functionalized ketene dithioacetals [3,5,6] and the tremendous applications of arynes in cyclization reactions, [7] we envisioned the palladiumcatalyzed CÀS activation as the key to developing an annulation between arynes and a-carbamoyl ketene dithioacetals (1; Scheme 1) by the insertion of an aryne into a C À S bond. Furthermore, the expected products are 2-quinolinones (3) which have provoked great interest in chemical and biological fields.[8] However, the challenge of this strategy lies in avoiding the addition of the strongly nucleophilic sulfur atom in the substrates to the arynes (Scheme 1 A), and instead favoring insertion of the arynes into the CÀS bond. [9,10] To the best of our knowledge, transition-metal-catalyzed CÀS bond cleavage for aryne insertion has been seldom reported.[10]Herein, we report that arynes can react with ketene dithioacetals by palladium-catalyzed C À S bond activation followed by cyclization to produce 2-quinolinones, but they remain inactive towards the nucleophilic S-containing group (Scheme 1 B). The new synthetic method is also highlighted by the versatile transformations of the 4-functionalized 2-quinolinones, which are not easily obtained starting from the cor...

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Ligand‐Enabled Triple CH Activation Reactions: One‐Pot Synthesis of Diverse 4‐Aryl‐2‐quinolinones from Propionamides

Deng

Gong

et al. 2014

Angewandte Chemie

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Palladium‐Catalyzed Enantioselective Intramolecular Hydroarylation of Alkynes To Form Axially Chiral 4‐Aryl 2‐Quinolinones

Cited by 17 publications

References 66 publications

Dearomatization of Fused Arenes Using Platinum‐Catalyzed Intramolecular Formation of Two CC Bonds

Dearomatization of Fused Arenes Using Platinum‐Catalyzed Intramolecular Formation of Two CC Bonds

Palladium‐Catalyzed CS Activation/Aryne Insertion/Coupling Sequence: Synthesis of Functionalized 2‐Quinolinones

Ligand‐Enabled Triple CH Activation Reactions: One‐Pot Synthesis of Diverse 4‐Aryl‐2‐quinolinones from Propionamides

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