Synthesis of 1-aryl-1,3-diyne and 2-aryl-1,1-dialkynylethene from the Sonogashira reactions of 2-aryl-1,1-dibromoethene

Lee, Hee Bong; Huh, Dal Ho; Oh, Joon Seok; Min, Gwan-Hong; Kim, Byung-Hyun; Lee, Dong Hwal; Hwang, Jae Kwang; Kim, Young Gyu

doi:10.1016/s0040-4020(01)00829-8

Cited by 19 publications

(6 citation statements)

References 18 publications

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“…Kim and co-workers systematically investigated the reaction conditions for the Sonogashira cross-coupling of 2-aryl-1,1-dibromoethenes with 1-alkynes . The coupling of the dibromide 316 with the alkyne 317 , chosen as a model substrate, was carried out under a variety of conditions, including Pd catalysts [PdCl 2 (PPh 3 ) 2 , Pd 2 (dba) 3 , Pd(OAc) 2 , PdCl 2 (PhCN) 2 , PdCl 2 , Pd(PPh 3 ) 4 ], phosphine ligands [PPh 3 , TFP, P(2-MeOC 6 H 4 ) 3 , dppb, P(4-MeOC 6 H 4 ) 3 ], solvents [benzene, toluene, ClCH 2 CH 2 Cl, TFP, AcOEt, acetone, MeCN, DMF, DMSO, NMP, n -BuOH], amines [Et 3 N, piperidine, pyrrolidine, morpholine, i -Pr 2 NH, Et 2 NH, t -BuNH 2 , n -BuNH 2 ], amount of the Pd catalyst, and reaction concentration (Scheme ).…”

Section: Metal-catalyzed Reactions Of Gem-dihalovinyl Systemsmentioning

confidence: 99%

Synthesis and Metal-Catalyzed Reactions of gem-Dihalovinyl Systems

2011

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Vinyl halides 24 and 25 were prepared from the tribromoromethyl carbinol 23, obtained in turn by reaction of benzo[b]thiophene-2-carboxaldehyde with the tribromomethane anion 43 generated in situ from 2,2,2-tribromoethanoic acid in DMSO (Scheme 24). 44 The intermediate 23 was treated with SOCl 2 or Et 2 NSF 3 to give the vinyl halides 24 (33% yield) or 25 (32% yield) through halogenation followed by dehydrobromination.2.1.3. Substitution Reactions. Although the most common source for gem-dibromoalkenes are carbonyl compounds, there are some examples in which alkene and alkyne derivatives have been used as starting materials. Reaction of longifolene 26 and camphene 29 with Hg(OAc) 2 /NaCl resulted in the isolation of vinylic dimercurichlorides 27 and 30, respectively (Scheme 25). These organometallics by treatment with Br 2 in pyridine afforded the related gem-dibromoalkenes 28 and 31 in very high yields. 45 Recently, 1,1-dibromo-2-arylethenes have been readily obtained in good yields (66À90%) via double ipso-bromo desilylation with N-bromosuccinimide (NBS) of 1,1-bis(trimethylsilyl)-2arylethenes, which were in turn easily obtained in high yields by Heck coupling of aryliodides with ethene-1,1-diylbis(trimethylsilane) (Scheme 26). 46 Interestingly, 1,1-bis(trimethylsilyl)-2-alkenylethenes, for example, 1,1-bis(trimethylsilyl)-4-phenylbuta-1,3-diene, under the same reaction conditions led to the selective formation of the dibrominated products containing 1,3-diene fragments.A variety of gem-dibromides were prepared from stannyl acetylenes (Scheme 27). These compounds by treatment with 1.4 equiv of Cp 2 Zr(H)Cl generated the related 1,1-heterobimetallic species of tin and zirconium, which by brominolysis with 2.5 equiv of Br 2 in CCl 4 or 3.0 equiv of N-bromosuccinimide at room temperature gave the corresponding dibromides in 53À83% yields. 47 2.1.4. Miscellaneous Reactions. Nenajdenko and co-workers reported an efficient one-pot transformation of a wide range of aldehydes and ketones into the corresponding dibromoalkenes via intermediate formation of the related hydrazones (Scheme 28). 48 Thus, these carbonyl compounds were treated with hydrazine hydrate, and when the starting materials disappeared, CBr 4 and catalytic CuCl were added to give the target products in 43À97% yields from aldehydes 48a and 43À97% yields from linear, cyclic, and caged ketones, 48a depending on the steric hindrance of the staring material. Analogously, a wide range of hydrazones of (hetero)aryl alkyl ketones (electron-rich and electron-poor) was converted into the related dibromoalkenes in 23À92% yields. 48b The proposed mechanism of the reaction starts from the oxidation of CuCl with CBr 4 to give a Cu(II) salt, which in turn oxidizes the hydrazone to the diazoalkane (Scheme 28). Decomposition of the diazoalkane generates a copperÀcarbene complex, which by interaction with CBr 4 finally leads to the dibromoalkene.

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Section: Metal-catalyzed Reactions Of Gem-dihalovinyl Systemsmentioning

confidence: 99%

Synthesis and Metal-Catalyzed Reactions of gem-Dihalovinyl Systems

2011

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“…In summary, a facile, mild, and general two-step homologation of aryl (alkenyl) aldehydes to the corresponding amides via 1,1-dibromo-1-alkenes was developed. To the best of our knowledge, the route reported here is the shortest and most convenient one to prepare homologated amides from aldehydes . This homologation could find a wide range of applications in medicinal chemistry in particular, as amides are one of the most common functional groups encountered.…”

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confidence: 95%

A Facile One-Carbon Homologation of Aryl Aldehydes to Amides

Shen

Kunzer

2002

Org. Lett.

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“…prop-2-yn-1-ol under particular optimized conditions [44,45], (iv) one-pot conversion of alcohol 1b into terminal alkynyl-coumarin [46] followed by cross-coupling reaction with 3-iodoprop-2-yn-1-ol and (v) oxidative hetero-coupling of terminal alkynyl-coumarin with prop-2-yn-1-ol [24], were fruitless.…”

Section: Resultsmentioning

confidence: 99%

New coumarin-[60]fullerene dyads connected by an alkynyl linkage: Synthesis and fluorescence studies. Evidence for efficient singlet–singlet energy transfer

et al. 2015

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a b s t r a c tTwo new coumarin-[60]fullerene dyads, in which an alkyne group covalently links C 60 to coumarin, are synthesized via 1,3-dipolar cycloaddition and spectroscopically characterized. Their photophysical properties in apolar (toluene) and polar (THF and benzonitrile) solvents are studied at room temperature, revealing the nature and polarity dependence of the excited-state interactions between the coumarin and C 60 moieties. In both dyads and in all solvents, a strong quenching of the coumarin emission by C 60 was observed. It mainly results from a fast and efficient singletesinglet resonance energy transfer from the coumarin moiety to the C 60 moiety, but an electron transfer contribution, enhanced in polar solvents, also exists. In toluene, the fluorescence emission of the fullerene moiety is increased by the nonradiative energy transfer process, which occurs mainly by a dipoleedipole (FRET) mechanism. In polar solvents (THF and benzonitrile), fast electron transfer from ground-state coumarin to excited fullerene is significant, leading to a partial or complete quenching of the fullerene emission, depending on the dyad.

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Synthesis of 1-aryl-1,3-diyne and 2-aryl-1,1-dialkynylethene from the Sonogashira reactions of 2-aryl-1,1-dibromoethene

Cited by 19 publications

References 18 publications

Synthesis and Metal-Catalyzed Reactions of gem-Dihalovinyl Systems

Synthesis and Metal-Catalyzed Reactions of gem-Dihalovinyl Systems

A Facile One-Carbon Homologation of Aryl Aldehydes to Amides

New coumarin-[60]fullerene dyads connected by an alkynyl linkage: Synthesis and fluorescence studies. Evidence for efficient singlet–singlet energy transfer

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