Elucidating Multicomponent Mechanisms in the Catalytic Hydrogenation of 2-Methylquinoline under Crude-H2 Conditions: A Key H2-Cleavage Process by a Boron−Olefin Lewis Pair DOI Creative Commons
Taiki Hashimoto, Yu Harabuchi, Sensuke Ogoshi

и другие.

Bulletin of the Chemical Society of Japan, Год журнала: 2024, Номер unknown

Опубликована: Дек. 30, 2024

Abstract The mechanisms of the triarylborane-catalyzed hydrogenation 2-methylquinoline (MeQin) in presence CO2 were investigated using artificial force induced reaction (AFIR) method. When B(C6F5)3 (B1) is used as catalyst, proceeds via intermolecular proton and hydride transfer from [MeQin‒H][H−B1] to a 1,4-dihydroquinoline intermediate (p-H2-MeQin). However, we confirmed that B1 quickly decomposes CO2-capture with 2-methyl-1,2,3,4-tetrahydroquinoline (H4-MeQin) followed by thermally proto-deboronation. B(2,6-Cl2C6H3)(3,5-Br2-2,6-F2C6H)2 (B2) employed, dissociation corresponding product can occur prior irreversible proto-deboronation step, MeQin thus continues efficiently. Moreover, AFIR analysis suggested frustrated Lewis pair (FLP) comprising boron atom B2 olefinic carbon p-H2-MeQin would mediate heterolytic cleavage H2. Based on these mechanistic details, identified modified catalyst B(2-Cl-6-FC6H3)3 (B7) demonstrates remarkable turnover number (TON = 4,000) under H2/CO2 conditions.

Язык: Английский

Elucidating Multicomponent Mechanisms in the Catalytic Hydrogenation of 2-Methylquinoline under Crude-H2 Conditions: A Key H2-Cleavage Process by a Boron−Olefin Lewis Pair DOI Creative Commons
Taiki Hashimoto, Yu Harabuchi, Sensuke Ogoshi

и другие.

Bulletin of the Chemical Society of Japan, Год журнала: 2024, Номер unknown

Опубликована: Дек. 30, 2024

Abstract The mechanisms of the triarylborane-catalyzed hydrogenation 2-methylquinoline (MeQin) in presence CO2 were investigated using artificial force induced reaction (AFIR) method. When B(C6F5)3 (B1) is used as catalyst, proceeds via intermolecular proton and hydride transfer from [MeQin‒H][H−B1] to a 1,4-dihydroquinoline intermediate (p-H2-MeQin). However, we confirmed that B1 quickly decomposes CO2-capture with 2-methyl-1,2,3,4-tetrahydroquinoline (H4-MeQin) followed by thermally proto-deboronation. B(2,6-Cl2C6H3)(3,5-Br2-2,6-F2C6H)2 (B2) employed, dissociation corresponding product can occur prior irreversible proto-deboronation step, MeQin thus continues efficiently. Moreover, AFIR analysis suggested frustrated Lewis pair (FLP) comprising boron atom B2 olefinic carbon p-H2-MeQin would mediate heterolytic cleavage H2. Based on these mechanistic details, identified modified catalyst B(2-Cl-6-FC6H3)3 (B7) demonstrates remarkable turnover number (TON = 4,000) under H2/CO2 conditions.

Язык: Английский

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