Sulfur ylide vinylation of halides and mesylates

Alcaraz, Lilian; Harnett, J. J.; Mioskowski, Charles; Martel, Jean-Philippe; Gall, Thierry Le; Shin, Dong Soo; Falck, John R.

doi:10.1016/s0040-4039(00)73523-4

Cited by 28 publications

(19 citation statements)

References 5 publications

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“…Preparation of the starting materials 1 a-1 h: The starting 1-aryl-1-alkynes 1 a-h were easily prepared by the reaction of arylethynyllithium with alkyl iodides [14] or the Sonogashira coupling of terminal alkynes with organic halides [15] (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Experimental and Theoretical Study of Tunable 1,3‐Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd‐Catalyzed Cross‐Coupling Reactions

Zhao

Liu

et al. 2009

Chemistry A European J

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The highly selective tuning of the isomerization from 1-arylalka-1,2-dien-1-yllithium to 1-arylalka-1,2-dien-3-yllithium has been realized in the deprotonation of 1-arylalk-1-yne (conditions A and B) and carbolithiation of 1-arylbut-3-en-1-yne with alkyllithium (conditions C and D). Subsequent transmetallation and Pd-catalyzed Negishi coupling reactions afforded 1,1-diaryl or 1,3-diaryl allenes with high selectivity. Deuterium-labeling cross experiments indicated that an intermolecular lithiation process occurred in both 1,3-lithium shift conditions (conditions B and D). 1-Arylalka-1,2-diene was confirmed experimentally to be the intermediate. A computational study at the B3LYP level for the isomerization indicated that the acidity of H at the 3-position is higher than that of the H at the 1-position of 1-phenyl-1,2-butadiene. Under conditions B, iPr(2)NH acts as a proton carrier to finish the 1,3-lithium shift. The overall activation barrier for the rate-determining step in the solvated models is approximately 21.0 kcal mol(-1), indicating that the isomerization is reasonable at room temperature. For the isomerization under conditions D, DFT calculations indicated that the addition of TMEDA (tetramethylethylenediamine) and HMPA (hexamethylphosphoramide) changes the global minimum of the system; among the possible mechanisms (P1-P5) considered, the mechanism catalyzed by dilithiated species (P5) is the most probable one. The overall activation barriers for isomerization in THF and TMEDA solvated models are 22.6 and 19.7 kcal mol(-1), respectively, proving that the isomerization may proceed at RT in THF or at -78 degrees C with TMEDA, due to the fact that the solvation of the additives may increase the concentration of 1-phenyl-1,2-butadienyllithium monomer by a deaggregation effect.

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Section: Resultsmentioning

confidence: 99%

Experimental and Theoretical Study of Tunable 1,3‐Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd‐Catalyzed Cross‐Coupling Reactions

Zhao

Liu

et al. 2009

Chemistry A European J

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“…[1][2][3][4][5] This class of intermediates has been found to have wide applications in the synthesis of epoxides, 6,7 cyclopropanes, 8 aziridines, [9][10][11] terminal alkenes, 12 and organoboron compounds. 13,14 The most common method of sulfur ylide generation consists of proton abstraction from the corresponding sulfonium salts, which are available by the direct alkylation of thioethers (Scheme 1, method A, path 1).…”

Section: Scheme 1 Preparation Of Sulfur Ylidesmentioning

confidence: 99%

The Epoxidation of Carbonyl Compounds with a Benzyne-Triggered Sulfur Ylide

et al. 2016

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An efficient method for the synthesis of epoxides from carbonyl compounds, sulfoxides, and benzyne is presented. The strategy involved an epoxidation by a sulfur ylide which is formed in situ from sulfoxide and benzyne through the S-O bond insertion and deprotonation. This one-pot reaction proceeds under mild and base-free conditions, providing a convenient way to introduce the substituted methylene groups onto the carbonyl carbon.

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“…3‐Pentylnona‐3,4‐dien‐2‐one (1 l) : The reaction of nona‐1‐en‐3‐yne28 (2.12 g, 16.5 mmol) with n PrLi (1.6 M in Et 2 O, 15 mmol) and N , N ‐dimethylacetamide (1.44 g, 16.5 mmol) afforded 1 l (2.04 g, 66 %). 1 H NMR (300 MHz, CDCl 3 ): δ =5.56–5.40 (m, 1 H; HCCC), 2.20 (s, 3 H; CH 3 ), 2.12–1.90 (m, 4 H, 2 CH 2 ), 1.45–1.08 (m, 10 H; 5 CH 2 ), 0.90–0.75 (m, 6 H; 2 CH 3 ); IR (neat): $\tilde \nu$ =1944 (CCC), 1679 cm −1 (CO); MS (70 eV): m/z (%): 208 (3.85) [ M + ], 43 (100) [C 3 H 7 + ]; HRMS: calcd for C 14 H 24 O: 208.1827; found: 208.1858.…”

Section: Methodsmentioning

confidence: 99%

Pd⁰‐Catalyzed Coupling Cyclization Reaction of Aryl or 1Alkenyl Halides with 1,2‐Allenyl Ketones: Scope and Mechanism. An Efficient Assembly of 2,3,4‐, 2,3,5‐Tri‐ and 2,3,4,5‐Tetrasubstituted Furans

Zhang

2003

Chemistry A European J

146

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Described herein is the Pd(0)-catalyzed coupling cyclization reaction of 1,2-allenyl ketones with organic halides leading efficiently and conveniently to not only 2,3,4- and 2,3,5-trisubstituted furans but also 2,3,4,5-tetrasubstituted furans. Furthermore, this method showed high substituent-loading capability and tolerance of various substituents. The reactions of 1,2-allenyl ketones 1 e, 1 p, 1 q, and deuterated [D]1 c were performed for a mechanistic study, which demonstrated that instead of an enolization pathway, the reaction may proceed via the intermediacy of dienolate palladium and intramolecular nucleophilic attack on the pi-allyl palladium intermediate by the carbonyl oxygen.

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Sulfur ylide vinylation of halides and mesylates

Cited by 28 publications

References 5 publications

Experimental and Theoretical Study of Tunable 1,3‐Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd‐Catalyzed Cross‐Coupling Reactions

Experimental and Theoretical Study of Tunable 1,3‐Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd‐Catalyzed Cross‐Coupling Reactions

The Epoxidation of Carbonyl Compounds with a Benzyne-Triggered Sulfur Ylide

Pd⁰‐Catalyzed Coupling Cyclization Reaction of Aryl or 1Alkenyl Halides with 1,2‐Allenyl Ketones: Scope and Mechanism. An Efficient Assembly of 2,3,4‐, 2,3,5‐Tri‐ and 2,3,4,5‐Tetrasubstituted Furans

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Sulfur ylide vinylation of halides and mesylates

Cited by 28 publications

References 5 publications

Experimental and Theoretical Study of Tunable 1,3‐Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd‐Catalyzed Cross‐Coupling Reactions

Experimental and Theoretical Study of Tunable 1,3‐Lithium Shift of Propargylic/Allenylic Species, Transmetallation, and Pd‐Catalyzed Cross‐Coupling Reactions

The Epoxidation of Carbonyl Compounds with a Benzyne-Triggered Sulfur Ylide

Pd0‐Catalyzed Coupling Cyclization Reaction of Aryl or 1Alkenyl Halides with 1,2‐Allenyl Ketones: Scope and Mechanism. An Efficient Assembly of 2,3,4‐, 2,3,5‐Tri‐ and 2,3,4,5‐Tetrasubstituted Furans

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Pd⁰‐Catalyzed Coupling Cyclization Reaction of Aryl or 1Alkenyl Halides with 1,2‐Allenyl Ketones: Scope and Mechanism. An Efficient Assembly of 2,3,4‐, 2,3,5‐Tri‐ and 2,3,4,5‐Tetrasubstituted Furans