Enantioselective Heck/Tsuji−Trost Reaction of Flexible Vinylic Halides with 1,3-Dienes DOI Creative Commons
Junliang Zhang, Li‐Zhi Zhang, Peichao Zhang

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Авг. 16, 2024

Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress relative rigid skeleton substrates, the implementation of asymmetric cascades highly flexible haloalkene substrates remains challenging and long-standing goal. Here we report an efficient tandem Heck/Tsuji−Trost reaction vinylic halides with 1,3-dienes enabled by palladium catalysis. A variety functional cyclic isoprenoids, which are key structural motifs numerous natural products family, were delivered good yields excellent regio-, diastereo- enantioselectivity. Specifically, Heck insertion stereodetermining step to form ƞ3 π-allyl complex situ trapping nucleophiles enable Heck/etherification formal (4+2) cycloaddition manner. Engineering Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands vital component achieving catalytic reactivity This strategy offers general, modular divergent platform rapidly upgrading feedstock dienes various value-added molecules is expected inspire development other Heck/cross-couplings.

Язык: Английский

Access to Cyclohexadiene and Benzofuran Derivatives via Catalytic Arene Cyclopropanation of α-Cyanodiazocarbonyl Compounds DOI

Mei-Lin Chen,

Chi-wen Chou,

Jia‐Liang Zhu

и другие.

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(27), С. 5552 - 5560

Опубликована: Янв. 1, 2024

Catalytic arene cyclopropanation of α-cyanodiazoacetates or α-diazo-β-ketonitriles gave norcaradienes dihydrobenzofurans, which were converted to cyclohexadienes benzofurans via cyclopropanation/reductive double ring-opening DDQ oxidation.

Язык: Английский

Процитировано

0
Organocatalytic Dearomative Spirocyclization Reaction of Enone-Tethered α-and β-Naphthols and Dearomatization Reaction of In Situ Generated Nitro-Olefin-Tethered α-Naphthols DOI

Amit Shikari,

Madhur Sharma,

Kalishankar Bhattacharyya

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(14), С. 9769 - 9782

Опубликована: Июнь 26, 2024

Herein, we report a catalytic dearomative spirocyclization reaction of new substrates having aryl/alkyl enone tethered α- and β-naphthols dearomatization in situ generated nitro-olefin-tethered α-naphthols. The spirocarbocycles were obtained moderate to good yields with high diastereoselectivities. A preliminary asymmetric variant was reported. few applications such as hydrogenations epoxidation have also been demonstrated. Theoretical study has performed understand diastereoselectivity the triethylamine catalyzed reaction.

Язык: Английский

Процитировано

0
Enantioselective Construction of Tetrahydroindole Skeletons by Rh‐Catalyzed [2+2+2] Cycloaddition of Homopropargyl Enamides with Alkynes DOI

Kairi Yamashiro,

Kohei Fujii, Yu Sato

и другие.

Angewandte Chemie, Год журнала: 2024, Номер 136(38)

Опубликована: Июнь 26, 2024

Abstract We have developed the Rh‐catalyzed enantioselective [2+2+2] cycloaddition of homopropargyl enamides (tosylamide‐tethered 1,6‐enynes) with alkynes to construct tetrahydroindole skeletons found in natural alkaloids and pharmaceuticals. This proceeds at room temperature high yields regio‐ enantioselectivity a broad substrate scope. The preparative scale reaction followed by substituent conversion on nitrogen atom diastereoselective [4+2] singlet O 2 affords hexahydroindole‐diols bearing three stereogenic centers variable substituents nitrogen. Mechanistic studies revealed that enynes change ratio intramolecular intermolecular rhodacycle formation when using terminal alkynes, varying ee values cycloadducts.

Язык: Английский

Процитировано

0
Enantioselective Heck/Tsuji−Trost Reaction of Flexible Vinylic Halides with 1,3-Dienes DOI Creative Commons
Junliang Zhang, Li‐Zhi Zhang, Peichao Zhang

и другие.

Research Square (Research Square), Год журнала: 2024, Номер unknown

Опубликована: Авг. 16, 2024

Abstract The enantioselective domino Heck/cross-coupling has emerged as a powerful tool in modern chemical synthesis for decades. Despite significant progress relative rigid skeleton substrates, the implementation of asymmetric cascades highly flexible haloalkene substrates remains challenging and long-standing goal. Here we report an efficient tandem Heck/Tsuji−Trost reaction vinylic halides with 1,3-dienes enabled by palladium catalysis. A variety functional cyclic isoprenoids, which are key structural motifs numerous natural products family, were delivered good yields excellent regio-, diastereo- enantioselectivity. Specifically, Heck insertion stereodetermining step to form ƞ3 π-allyl complex situ trapping nucleophiles enable Heck/etherification formal (4+2) cycloaddition manner. Engineering Sadphos bearing androgynous non-C2-symmetric chiral sulfinamide phosphine ligands vital component achieving catalytic reactivity This strategy offers general, modular divergent platform rapidly upgrading feedstock dienes various value-added molecules is expected inspire development other Heck/cross-couplings.

Язык: Английский

Процитировано

0