Pd-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions between Sulfamates and Potassium Boc-Protected Aminomethyltrifluoroborates

Molander, Gary A.; Shin, Inji

doi:10.1021/ol401021x

Cited by 43 publications

(11 citation statements)

References 23 publications

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“…45 For example, phenol-containing moieties are intermediates in many target-oriented syntheses and can be used as coupling partners after activation when analogous halides would be difficult to access. 46 Additionally, in some cases phenol derivatives can act as directing groups for prefunctionalization of the aromatic backbone of the electrophile through directed ortho-metalation prior to crosscoupling. 47 Although simple phenol derivatives such as aryl sulfonates (e.g., triflates, mesylates, and tosylates) are often used in cross-coupling, 45b,48 these moieties are not useful directing groups.…”

Section: New Substrates For Traditionalmentioning

confidence: 99%

Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

2018

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Cross-coupling reactions, which were discovered almost 50 years ago, are widely used in both industry and academia. Even though cross-coupling reactions now represent mature technology, there is still a significant amount of research in this area that aims to improve the scope of these reactions, develop more efficient catalysts, and make reactions more practical. In this tutorial, a brief background to cross-coupling reactions is provided, and then the major advances in crosscoupling research over the last 20 years are described. These include the development of improved ligands and precatalysts for cross-coupling and the extension of cross-coupling reactions to a much wider range of electrophiles. For example, cross-coupling reactions are now common with sp 3 -hybridized electrophiles as well as ester, amide, ether, and aziridine substrates. For many of these more modern substrates, traditional palladium-based catalysts are less efficient than systems based on first-row transition metals such as nickel. Conventional cross-coupling reactions have also inspired the development of a range of related reactions, such as cross-electrophile and decarboxylative couplings as well as couplings based on metallaphotoredox chemistry. The development of these new reactions is probably at the same stage as traditional cross-coupling reactions 30 years ago, and this tutorial highlights how many of the same strategies used to improve cross-coupling reactions may also be applicable to making the new reactions more practical.

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Section: New Substrates For Traditionalmentioning

confidence: 99%

Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

2018

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“…Molander has performed extensive studies on aromatic aminomethylations using a variety of substituted R 2 NCH 2 BF 3 K salts by Pd-or photoredox/Ni-catalysis. 3 Pd-catalyzed aminobenzylations of branched aminoboronates were pioneered by the group of Suginome. 4 Additionally, Rh(I)-catalyzed additions to carbonyls were reported by Ellman, 5 and transition metal-free arylations of cyclic aminoboronates were recently disclosed by Aggarwal.…”

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confidence: 99%

Exploiting the Bis-Nucleophilicity of α-Aminoboronates: Copper-Catalyzed, Intramolecular Aminoalkylations of Bromobenzoyl Chlorides

2016

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α-Aminoboronate salts are interesting examples of heteroatomic species containing adjacent nucleophilic centers. We have developed an acylation/arylation reaction using 2-bromobenzoyl chlorides as bis-electrophiles that harnesses the nucleophilicity of both positions, leading to isoindolinones. The reactions proceed under mild conditions via an intramolecular, Cu-catalyzed sp(3)-sp(2) coupling, giving products in up to 95% yield. These conditions enable arylation of α,α-disubstituted aminoboronates, which are difficult to accomplish using methods based on less abundant and more expensive transition metals.

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“…Regarding the use of organoboranes other than the classic boronic acids and esters, Molander reported the coupling of potassium 1-(benzyloxy)alkyltrifluoroborates with aryl and heteroaryl chlorides [18] potassium Boc-protected aminomethyltrifluoroborates with aryl and heteroaryl mesylates [19] and sulfamates [20] and potassium cyclopropyl- and alkoxymethyltrifluoroborates with benzyl chlorides [21], using commercially available phosphines like RuPhos or SPhos (Scheme 1, Reactions (1)–(4)). Buchwald demonstrated that lithium triisopropyl borate salts can be used in SMR, and even devised a one-pot lithiation/borylation/SMR for the coupling of heteroarenes using complex 1 (Figure 1) as pre-catalyst (Scheme 1, Reaction (5)) [22].…”

Section: Catalytic Systemsmentioning

confidence: 99%

Recent Developments in the Suzuki-Miyaura Reaction: 2010–2014

2015

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Abstract:The Suzuki-Miyaura reaction (SMR), involving the coupling of an organoboron reagent and an organic halide or pseudo-halide in the presence of a palladium or nickel catalyst and a base, has arguably become one of most utilized tools for the construction of a C-C bond. This review intends to be general account of all types of catalytic systems, new coupling partners and applications, including the

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Pd-Catalyzed Suzuki–Miyaura Cross-Coupling Reactions between Sulfamates and Potassium Boc-Protected Aminomethyltrifluoroborates

Cited by 43 publications

References 23 publications

Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

Cross-Coupling and Related Reactions: Connecting Past Success to the Development of New Reactions for the Future

Exploiting the Bis-Nucleophilicity of α-Aminoboronates: Copper-Catalyzed, Intramolecular Aminoalkylations of Bromobenzoyl Chlorides

Recent Developments in the Suzuki-Miyaura Reaction: 2010–2014

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