Pd-Catalyzed Asymmetric Dearomatization of Indoles via Decarbonylative Heck-Type Reaction of Thioesters

Han, Ming-Liang; Huang, Wei; Liu, Yuwen; Liu, Min; Xu, Hui; Xiong, Hai; Dai, Hui‐Xiong

doi:10.1021/acs.orglett.0c03897

Cited by 41 publications

(13 citation statements)

References 85 publications

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“… [4–6] The majority of these reactions were performed in an intramolecular manner (Scheme 1a), in which a haloarene or an acetylene is tethered to the N1‐, C2‐ or C3‐position of indole as the C(sp 2 )–Pd precursor. The You group achieved enantioselective C3‐arylation of C3‐tethered indoles; [4p] Jia [4b,k] and Fukuyama [4n] developed the dearomative Heck reaction of N1‐ and C2‐tethered indoles to build a C2‐stereocenter; Jia, [4h–j,m,o] Liang, [4c,d] Lautens, [4h] and Dai [4e] reported the asymmetric dearomative difunctionalization of N1‐tethered indoles by employing an external nucleophile.…”

Section: Methodsmentioning

confidence: 99%

Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium‐Catalyzed Asymmetric Dearomatization of Indoles**

Gao

Jiao

2022

Angewandte Chemie

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Dearomatized indole derivatives bearing a C3‐ or C2‐stereocenter exist ubiquitously in natural products and biologically active molecules. Despite remarkable advances in their synthesis, stereoselective and regio‐divergent methods are still in a high demand. Herein, a Pd‐catalyzed intermolecular asymmetric spiroannulation of 2,3‐disubstituted indoles with internal alkynes has been developed for the efficient construction of indoline structures with a C2‐quaternary stereocenter. Stereospecific aza‐semipinacol rearrangement of these indoline derivatives under acidic conditions afforded indolenine products bearing a C3‐quaternary stereocenter, where the migrating group could be controlled by the reaction sequence. The asymmetric spiroannulation together with the subsequent aza‐semipinacol rearrangement enabled a divergent access to dearomatized indole derivatives with either a C3‐ or a C2‐quaternary stereocenter.

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Section: Methodsmentioning

confidence: 99%

Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium‐Catalyzed Asymmetric Dearomatization of Indoles**

Gao

Jiao

2022

Angewandte Chemie

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“…More recent efforts have focused on the dearomatization of indoles through the aid of transition-metal catalysis. − Many of these processes take advantage of the inherent nucleophilicity of indole to direct the regioselectivity of the dearomatization . However, an alternative approach that is not reliant on adding electrophiles to C3 and nucleophiles to C2 involves a migratory insertion of the C2–C3 π-bond of indole into a [M]-R bond to access diverse indoline products (Scheme C) .…”

Section: Introductionmentioning

confidence: 99%

“…However, an alternative approach that is not reliant on adding electrophiles to C3 and nucleophiles to C2 involves a migratory insertion of the C2–C3 π-bond of indole into a [M]-R bond to access diverse indoline products (Scheme C) . The intramolecular version of this strategy has been advanced in a series of elegant studies from Jia, Lautens, and others . While the selectivity of these reactions is not reliant on inherent reactivity, the tether dictates the regiochemical outcome of the reaction.…”

Section: Introductionmentioning

confidence: 99%

Nickel-Catalyzed Dearomative Arylboration of Indoles: Regioselective Synthesis of C2- and C3-Borylated Indolines

et al. 2021

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Indole dearomatization is an important strategy to access indolines: a motif present in a variety of natural products and biologically active molecules. Herein, a method for transition-metal catalyzed regioselective dearomative arylboration of indoles to generate diverse indolines is presented. The method accomplishes intermolecular dearomatization of simple indoles through a migratory insertion pathway on substrates that lack activating or directing groups on the C2- or C3-positions. Synthetically useful C2- and C3-borylated indolines can be accessed through a simple change in N-protecting group in high regio- and diastereoselectivities (up to >40:1 rr and >40:1 dr) from readily available starting materials. Additionally, the origin of regioselectivity was explored experimentally and computationally to uncover the remarkable interplay between carbonyl orientation of the N-protecting group on indole, electronics of the C2–C3 π-bond, and sterics. The method enabled the first enantioselective synthesis of (−)-azamedicarpin.

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“…This property is exploited by nature in the form of acetyl-CoA, which carries out acetylation to aid the metabolic pathways of biological components such as fatty acids, peptides, sterols, terpenes, and porphyrins . The diverse reactivity profile of the thioesters, while being bench-stable reagents, has intrigued synthetic chemists to employ these moieties in decarbonylation, coupling reactions, reduction, photoredox catalysis, and C(O)–S bond cleavage and acyl transfer reactions …”

Section: Introductionmentioning

confidence: 99%

Visible-Light-Mediated Cross Dehydrogenative Coupling of Thiols with Aldehydes: Metal-Free Synthesis of Thioesters at Room Temperature

2021

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Thioesters play a crucial role in biological systems and serve as important building blocks for organic synthesis. Herein, Eosin Y and TBHP mediated photochemical cross dehydrogenative coupling (PCDC) between feedstock aldehydes and thiols has been described at room temperature to synthesize thioesters. This thioesterification protocol proceeds smoothly to give the desired products in good to excellent yields by the suitable PCDC of both alkyl/aryl- aldehydes with a variety of alkyl/aryl-thiols and generates water and t BuOH as green byproducts. This method is also found to be scalable with good efficiency. Mechanistic investigations reveal that under this photochemical condition, the formation of acyl radical can be achieved from aldehyde. This acyl radical was further intercepted with an intermediate disulfide, generated in situ via the dehydrogenation of thiol to give the desired thioester. Moreover, disulfides, which are relatively easier to handle, also provided good to excellent yields in the optimized reaction condition. This protocol was further extended toward the more challenging direct transformation of alcohols to thioesters.

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Pd-Catalyzed Asymmetric Dearomatization of Indoles via Decarbonylative Heck-Type Reaction of Thioesters

Cited by 41 publications

References 85 publications

Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium‐Catalyzed Asymmetric Dearomatization of Indoles**

Divergent Synthesis of Indolenine and Indoline Ring Systems by Palladium‐Catalyzed Asymmetric Dearomatization of Indoles**

Nickel-Catalyzed Dearomative Arylboration of Indoles: Regioselective Synthesis of C2- and C3-Borylated Indolines

Visible-Light-Mediated Cross Dehydrogenative Coupling of Thiols with Aldehydes: Metal-Free Synthesis of Thioesters at Room Temperature

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