Palladium-Catalyzed Hiyama Cross-Coupling of Aryltrifluorosilanes with Aryl and Heteroaryl Chlorides

Molander, Gary A.; Iannazzo, Laura

doi:10.1021/jo201840n

Cited by 46 publications

(24 citation statements)

References 48 publications

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“…The organic layer was combined, washed with brine, and dried over anhydrous Na 2 SO 4 .S olvent was removed and the residue was purified by column chromatography (hexane/ethyl acetate = 10:1, R f = 0.7) to afford 7 as ac olorless liquid (2.16 g, 13 mmol). [26] 2,6-Bis(bromomethyl)-4-methoxy-1,1'-biphenyl (2 a):T oasolution of 9 (1.4 g, 6.6 mmol) in benzene (50 mL), N-bromosuccinimide (2.35 g, 13.2 mmol) and azobisisobutyronitrile (108 mg, 0.66 mmol) were added, and the reaction mixture was heated to reflux for 2h. [24] 1,3-Bis(bromomethyl)-2,5-dimethoxybenzene (1 a):T oasolution of 7 (1.66 g, 10 mmol) in benzene (40 mL), N-bromosuccinimide (3.56 g, 20 mmol) and azobisisobutyronitrile (164.21 mg, 1mmol) were added and the reaction mixture was heated to reflux for 3h.…”

Section: Methodsmentioning

confidence: 99%

Substituents Have a Large Effect on Photochemical Generation of Benzyl Cations and DNA Cross‐Linking

Fan

Sun

Peng

2018

Chemistry A European J

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Photoactivated DNA interstrand cross-linking agents have a wide range of biological applications. Recently, several aryl boronates have been reported to induce DNA interstrand cross-link (ICL) formation via carbocations upon photoirradiation. Herein, we synthesized a series of new bifunctional phenyl compounds to test the generality of such a mechanism, and to understand how the chemical structure influences carbocation formation and the DNA cross-linking process. These compounds efficiently form DNA ICLs via generated benzyl cations upon 350 nm irradiation. The DNA cross-linking efficiency and the pathway for carbocation generation depend on both the aromatic substituents and the leaving groups. Bromine as a leaving group facilitates the DNA cross-linking process in comparison with trimethyl ammonium salt. Both electron-donating and -withdrawing substituents induce bathochromic shifts, which favor photoinduced DNA ICL formation. For the bromides, the benzyl cation intermediates were generated through oxidation of the corresponding benzyl radicals. However, for the ammonia salts, the benzyl cations were formed through two pathways: either through oxidation of the benzyl radicals or by direct heterolysis of the C-N bond. Photoinduced C-N homolysis to form benzyl radicals occurred with compounds having donating substituents, whereas direct heterolysis of the C-N bond occurred with those bearing withdrawing substituents. The adducts formed between 1 a and four natural nucleosides were characterized, indicating that the alkylation sites for the photogenerated benzyl cations are dG, dA, and dC.

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Section: Methodsmentioning

confidence: 99%

Substituents Have a Large Effect on Photochemical Generation of Benzyl Cations and DNA Cross‐Linking

Fan

Sun

Peng

2018

Chemistry A European J

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“…In connection with our recent efforts on the development of Cu-catalyzed 1,4-additions [14] and on the use of organosilicon reagents, [15] we report herein a general method for the conjugate silylation of various α,β-unsaturated compounds using disilanes (Scheme 1). …”

Section: Introductionmentioning

confidence: 99%

“…[8] However, despite the efficiency of the activation of the Si-B bond [9] by transition metals (Cu, Rh) [10,11] or N-heterocyclic carbenes, [12] this approach suffers from a lack of atom economy, [13] as these reagents required an additional step for their synthesis. [7] In connection with our recent efforts on the development of Cu-catalyzed 1,4-additions [14] and on the use of organosilicon reagents, [15] we report herein a general method for the conjugate silylation of various α,β-unsaturated compounds using disilanes (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Activation of Si–Si Bonds for Copper(I)‐Catalyzed Conjugate Silylation

Iannazzo

Molander

2012

Eur J Org Chem

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Several alkyl- and vinylsilanes were prepared through the copper(I)-catalyzed conjugate silylation of α,β-unsaturated compounds. Optimal reaction conditions were first investigated to realize the conjugate addition of a nucleophilic silicon species to poorly electrophilic acceptors such as phenylvinyl sulfone by cleavage of the Si–Si bond of a disilane reagent. The scope of this reaction was extended to various electrophiles bearing different electron-withdrawing groups and afforded the desired substituted alkyl- and vinylsilanes. Among the wide range of commercially available disilanes, the reactivities of alkyl-, aryl-, and ethoxydisilane were also examined.

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“…The use of reagents of type Ar1SiF 3 ( 7 ) has been reported for the palladium‐catalyzed cross‐coupling with aryl or heteroaryl chlorides in the presence of the phosphine XPhos as ligand and tetrabutylammonium fluoride (TBAF) as a fluoride source, giving the expected products 8 (Scheme ) 8…”

Section: Arylation Reactionsmentioning

confidence: 99%

The Hiyama Cross‐Coupling Reaction: New Discoveries

Foubelo

Nájera

Yus

2016

The Chemical Record

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ABSTRACT:In this review article recent developments in the Hiyama cross-coupling reaction from 2010 up today are presented. The most important methodology involves formation of biaryl systems by using aryl bromides or iodides and aryl trialkoxy silanes: other variants are far less studied. The most useful procedures are collected paying special attention to the synthetic application of this methodology in synthetic organic chemistry.

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Palladium-Catalyzed Hiyama Cross-Coupling of Aryltrifluorosilanes with Aryl and Heteroaryl Chlorides

Cited by 46 publications

References 48 publications

Substituents Have a Large Effect on Photochemical Generation of Benzyl Cations and DNA Cross‐Linking

Substituents Have a Large Effect on Photochemical Generation of Benzyl Cations and DNA Cross‐Linking

Activation of Si–Si Bonds for Copper(I)‐Catalyzed Conjugate Silylation

The Hiyama Cross‐Coupling Reaction: New Discoveries

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