The first palladium-catalyzed Sonogashira coupling of unactivated secondary alkyl bromides

Altenhoff, Gereon; Würtz, Sebastian; Glorius, Frank

doi:10.1016/j.tetlet.2006.02.111

Cited by 203 publications

(109 citation statements)

References 36 publications

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“…Without FeBr 2 added, no product was obtained (Table S1, entry 21). The variation of other solvents and additives, however, did not further enhance the yield or even decreased the yield (Table S1, entries [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38]. Additionally, the use of transition metal salts other than iron salts did not catalyze the reaction (Table S1, entries 39-48).…”

Section: S5mentioning

confidence: 99%

Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

Cheung

Ren

2014

Org. Lett.

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A simple protocol for iron-catalyzed cross-coupling of nonactivated secondary alkyl bromides and iodides with alkynyl Grignard reagents at room temperature has been developed. A wide range of secondary alkyl halides and terminal alkynes are tolerated to afford the substituted alkynes in good yields. A slight modification of the reaction protocol also allows for cross-coupling with a variety of primary alkyl halides.

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Section: S5mentioning

confidence: 99%

Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

Cheung

Ren

2014

Org. Lett.

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“…Although aliphatic alcohols could not be used (not shown), aliphatic acids worked well in the reaction and full conversion and good yields were obtained after [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. In this case, the presence of -hydrogen on the double bond was not deleterious to the yield and even simple commercially available 4-pentenoic acid could be cyclized in good yield (Entry 20).…”

Section: Scheme 1 Wacker Cyclization and Alkoxyalkynylation Reactionmentioning

confidence: 99%

“…11 The Pd-catalyzed C-C bond formation between a SP 3 and a SP center is also a difficult process, which was successful only in rare cases. 12 Our report constitutes the first example of intramolecular oxyalkynylation of non-activated alkenes, which represents an important breakthrough in the area of oxidative Pd chemistry. The discovery of the unique This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, copyright © American Chemical Society after peer review and technical editing by the publisher.…”

mentioning

confidence: 91%

“…11 The Pd-catalyzed C-C bond formation between a SP 3 and a SP center is also a difficult process, which was successful only in rare cases. 12 Our report constitutes the first example of intramolecular oxyalkynylation of non-activated alkenes, which represents an important breakthrough in the area of oxidative Pd chemistry. The discovery of the unique superiority of benziodoxolone derived reagents 3c-3e for alkynyl transfer when compared with established alkynyliodonium salts (3a, 3b) constitutes an important advance in the burgeoning field of hypervalent iodine chemistry 13 and opens new perspective for the development of more efficient reagents in Pd-mediated C-C bond formation and other acetylene transfer processes.…”

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confidence: 91%

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Pd-Catalyzed Intramolecular Oxyalkynylation of Alkenes with Hypervalent Iodine

et al. 2009

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The first example of intramolecular oxyalkynylation of non-activated alkenes using oxidative Pd chemistry is reported. Both phenol and aromatic or aliphatic acid derivatives could be used under operator friendly conditions (room temperature, technical solvents, under air). The discovery of the superiority of benziodoxolone-derived hypervalent iodine reagent 3d as alkyne transfer reagent further expands the rapidly increasing utility of hypervalent iodine reagents in catalysis and is expected to have important implications for other similar processes.Cyclic structures are ubiquitous in natural products and other bioactive substances. 1 Consequently, the efficient synthesis of carbo-and hetero-cycles is an important field of research in organic chemistry. Metal-catalyzed cyclization reactions, especially when involving multiple C-C or C-X bond formations, constitute an efficient pathway to heterocycles. 2 One such method is the Wacker cyclization, which is the Pd catalyzed cyclization of nucleophiles on double bonds (Scheme 1, A). 2c,3 In place of -hydride elimination, further C-C, 2c,4 C-O, 5 C-N 6 and C-Cl 7 bond formation together with cyclization have been reported. 8 In particular, C-O and C-N bond formations have profited tremendously from the use of hypervalent iodine reagents as oxidants. 5,6 In contrast, C-C bond formation has been limited to SP 2 hybridized vinyl, carbonyl and aryl groups; none of these methods reported the use of hypervalent iodine reagents. 2c,4 It was recently demonstrated that oxidation of Pd(II) intermediates with aryliodonium salts was much slower than with PhI(OAc)2, which would make C-C bond formation unable to compete with other side reactions. 8b Herein, we report a Pd-catalyzed Wacker cyclization-alkynylation domino process using a benziodoxolone-derived reagent 3d (Scheme 1, B).Acetylenes have broad utility in organic chemistry, biological chemistry and material sciences. 9 Furthermore, the direct addition of acetylenes to non-activated olefins is challenging, and has been successful only for strained olefins 10 or using radical methods. 11 The Pd-catalyzed C-C bond formation between a SP 3 and a SP center is also a difficult process, which was successful only in rare cases. 12 Our report constitutes the first example of intramolecular oxyalkynylation of non-activated alkenes, which represents an important breakthrough in the area of oxidative Pd chemistry. The discovery of the unique This document is the Accepted Manuscript version of a Published Work that appeared in final form in Organic Letters, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/ ol9027286. superiority of benziodoxolone derived reagents 3c-3e for alkynyl transfer when compared with established alkynyliodonium salts (3a, 3b) constitutes an important advance in the burgeoning field of hypervalent iodine chemistry 13 and opens new perspective for the development of ...

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“…IBiox has been prepared by the Glorius group. 8 Ligands of the CAAC type have been introduced by the Bertrand group. 9,10 These ligands stand out due to their "flexible steric bulk", which enables them to influence transition metal catalysts' activities.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of an extremely sterically shielding N-heterocyclic carbene ligand

Weber¹,

Loos²,

Röminger³

et al. 2012

Arkivoc

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The N-heterocyclic carbene (NHC) ligand IPr** features substituents of unprecedented steric demand (IPr** = 1,3-bis[2,6-bis[(4-tert-butylphenyl)methyl]-4-methylphenyl]imidazol-2-ylidene). The NHC structure is an advanced derivative of the IPr system, and of the IPr* by Berthon-Gelloz and Markó. In the IPr** ancillary ligand, two para-methyl are introduced and eight methyl groups of IPr are formally replaced by a 4-tert-butylphenyl substituent, respectively, thereby sterically shielding both a coordinated metal and its second ligand. Favorable features of ligand and late transition metal complexes include high solubility, aesthetic NMR spectra, and a tendency towards crystallization.

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The first palladium-catalyzed Sonogashira coupling of unactivated secondary alkyl bromides

Cited by 203 publications

References 36 publications

Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

Mild and Phosphine-Free Iron-Catalyzed Cross-Coupling of Nonactivated Secondary Alkyl Halides with Alkynyl Grignard Reagents

Pd-Catalyzed Intramolecular Oxyalkynylation of Alkenes with Hypervalent Iodine

Synthesis of an extremely sterically shielding N-heterocyclic carbene ligand

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