Nickel-Catalyzed Arylboration of Cyclopentene

Sardini, Stephen R.; Brown, M. Kevin

doi:10.15227/orgsyn.097.0355

Cited by 9 publications

(4 citation statements)

References 2 publications

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“…It is proposed that the reversal of regioselectivity is the result of addition of the [Ni(I)]-Bpin to the C2–C3 π-bond to minimize steric pressure between the Bpin unit and the C2 substituent. Formation of a tertiary alkyl-[Ni] complex is rare , and this species is likely stabilized by both the α-aryl and α-carbamate groups. , With respect to the limitations, 3-phenyl indole was unreactive and alkyl substituents were not tolerated at the C2 and C3 positions.…”

Section: Resultsmentioning

confidence: 99%

“…Recently, our group has developed a Ni-catalyzed 1,2-arylboration reaction of alkenes. , On the basis of the principles learned, we envisioned advancing this area to the challenging problem of dearomatization. In particular, dearomative arylboration of indoles without the aid of activating or directing groups at C2/3 was undertaken, as it would allow for exploration of unprecedented and challenging reactivity .…”

Section: Introductionmentioning

confidence: 99%

“…Mechanistically, we hypothesized that [Ni(I)]-Bpin complex II would form through base-assisted transmetalation with B 2 pin 2 (Scheme ), followed by syn -addition across the C2–C3 π-bond of indole to generate two possible regioisomers ( III or IV ) . Reaction with the arylbromide electrophile would form arylboration product V or VI .…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2021

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“…[293] An importance of the method is confirmed by the fact that currently, it is referenced in Organic Syntheses. [294] Most importantly, the method was applicable to non-activated alkenes. In 2019, Liu, Brown, and co-workers described Ni-catalyzed arylboration of various monosubstituted, 1,1-disubstituted, and trisubstituted alkenes (Scheme 68 A and B).…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

Volochnyuk

Gorlova

Grygorenko

2021

Chemistry A European J

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This review discusses recent advances in the chemistry of saturated boronic acids, boronates, and trifluoroborates. Applications of the title compounds in the design of boron-containing drugs are surveyed, with special emphasis on α-amino boronic derivatives. A general overview of saturated boronic compounds as modern tools to construct C(sp 3 )À C and C(sp 3 )-heteroatom bonds is given, including recent developments in the Suzuki-Miyaura and Chan-Lam cross-couplings, single-electron-transfer processes including metallo-and organocatalytic photoredox reactions, and transformations of boron "ate" complexes. Finally, an attempt to summarize the current state of the art in the synthesis of saturated boronic acids, boronates, and trifluoroborates is made, with a brief mention of the "classical" methods (transmetallation of organolithium/magnesium reagents with boron species, anti-Markovnikov hydroboration of alkenes, and the modification of alkenyl boron compounds) and a special focus on recent methodologies (boronation of alkyl (pseudo)halides, derivatives of carboxylic acids, alcohols, and primary amines, boronative CÀ H activation, novel approaches to alkene hydroboration, and 1,2-metallate-type rearrangements).

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Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N‐Heterocycles

et al. 2022

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Two catalytic systems have been developed for the arylboration of endocyclic enecarbamates to deliver synthetically versatile borylated saturated N‐heterocycles in good regio‐ and diastereoselectivities. A Cu/Pd dual catalytic reaction enables the synthesis of borylated, α‐arylated azetidines, while a Ni‐catalysed arylboration reaction efficiently functionalizes 5‐, 6‐, and 7‐membered enecarbamates. In the case of the Cu/Pd‐system, a remarkable additive effect was identified that allowed for broader scope. The products are synthetically useful, as demonstrated by manipulations of the boronic ester to access biologically active compounds.

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Nickel-Catalyzed Arylboration of Cyclopentene

Cited by 9 publications

References 2 publications

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

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

Saturated Boronic Acids, Boronates, and Trifluoroborates: An Update on Their Synthetic and Medicinal Chemistry

Arylboration of Enecarbamates for the Synthesis of Borylated Saturated N‐Heterocycles

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