Stereoselective Synthesis of<i>Z</i>Alkenyl Halides via Julia Olefination

Lebrun, Marie-Eve; Marquand, Paul Le; Berthelette, Carl

doi:10.1021/jo052370h

Cited by 57 publications

(21 citation statements)

References 26 publications

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“…Among the tetrazolyl derivatives, 1-phenyl-1 H -tetrazol-5-yl n -alkyl sulfones have shown higher E -selectivity in condensation reactions compared to the tert -butyl analogues 7,16. Further, synthesis of α-bromo and α-chloromethyl 1-phenyl-1 H -tetrazol-5-yl sulfones and condensation reactions with aldehydes have recently been reported 18. These results led us to pursue the synthesis and fluorination of alkyl 1-phenyl-1 H -tetrazol-5-yl sulfones.…”

Section: Resultsmentioning

confidence: 98%

Fluorinated 1-Phenyl-1H-tetrazol-5-yl Sulfone Derivatives as General Reagents for Fluoroalkylidene Synthesis

Ghosh

Zajc

2009

J. Org. Chem.

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Julia-Kocienski olefination reagents 1-fluoropropyl, (cyclopropyl)fluoromethyl, 1-fluoro-2-methyl-2-propenyl and 1-fluoro-5-hexenyl 1-phenyl-1H-tetrazol-5-yl (PT) sulfones were prepared by metalation followed by electrophilic fluorination. Although metalation-fluorination of n-propyl, 5-hexenyl and (cyclopropyl)methyl PT-sulfones proceeded under homogeneous conditions, fluorination of 2-methyl-2-propenyl PT-sulfone required heterogeneous fluorination conditions. Condensation reactions of fluoro PT-sulfones with aldehydes resulted in fluoroalkylidenes in high yields. Screening of olefination conditions showed that stereoselectivity depended on reagent and carbonyl structure and can in many cases be tuned either towards E-or Z-selectivity. For example, LHMDS-mediated condensations of 1-fluoropropyl PT-sulfone in the presence of MgBr 2 ·OEt 2 were Z-selective with electron-rich aromatic aldehydes, a hindered aromatic aldehyde and cinnamaldehyde. Low temperature KHMDS-mediated condensations were E-selective with electron-rich and electron-deficient aromatic aldehydes and Z-selective with n-octanal. Dialkyl, aryl alkyl and diaryl ketones reacted as well to give fluoro olefin products in 71-99% yields.

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Section: Resultsmentioning

confidence: 98%

Fluorinated 1-Phenyl-1H-tetrazol-5-yl Sulfone Derivatives as General Reagents for Fluoroalkylidene Synthesis

Ghosh

Zajc

2009

J. Org. Chem.

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“…For pyridyl substrate 5d, the chloromethyl sulfide was obtained in one step by alkylation of mercaptopyridine 4d with NaH and chloroiodomethane in DMF. 28 Chloromethyl sulfides 5 were then used to alkylate ethylene glycol. Ethylene glycol was employed as a solvent, which avoided double alkylation and provided S,O-acetals 6a-k. Tosylation of the primary alcohol followed by oxidation with excess mCPBA to the corresponding sulfones afforded the cyclisation precursors 2 in high yields.…”

Section: Synthesis Of 2-(arylsulfonyl)oxetane Derivativesmentioning

confidence: 99%

Studies on the synthesis, stability and conformation of 2-sulfonyl-oxetane fragments

2015

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2-(Arylsulfonyl)oxetanes have been prepared as new structural motifs of interest for medicinal chemistry. These are designed to fit within fragment space and be suitable for screening in fragment based drug discovery, as well as being suitable for further elaboration or incorporation into drug-like compounds. The oxetane ring is constructed through an efficient C-C bond forming cyclisation which allows the incorporation of a wide range of aryl-sulfonyl groups. Furthermore, biaryl-containing compounds can be accessed through Suzuki-Miyaura coupling from halogenated derivatives. With a number of oxetane containing fragment compounds available, their pH stability was assessed, indicating good half-life values for mono-substituted aryl sulfonyl oxetanes across the pH range (1 to 10). Solubility and metabolic stability data is also reported. Finally, the conformation of the fragments is assessed computationally, providing an indication of possible binding orientations.

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“…Vinyl halides, in particular, are versatile substrates in many useful organic transformations including the well-known Stille, Suzuki, and Sonogashira coupling reactions [4][5][6][7][8][9][10]. The importance of vinyl halides in organic synthesis has stimulated a great deal of interest and much attention has been devoted to the synthesis of vinyl halides and their derivatives [11][12][13][14][15][16].…”

Section: Introductionmentioning

confidence: 99%

Regio- and stereospecific synthesis of vinyl halides via carbozincation of acetylenic sulfones followed by halogenation

Xie¹,

Wang²,

Zhang³

et al. 2009

Journal of Organometallic Chemistry

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Stereoselective Synthesis ofZAlkenyl Halides via Julia Olefination

Cited by 57 publications

References 26 publications

Fluorinated 1-Phenyl-1H-tetrazol-5-yl Sulfone Derivatives as General Reagents for Fluoroalkylidene Synthesis

Fluorinated 1-Phenyl-1H-tetrazol-5-yl Sulfone Derivatives as General Reagents for Fluoroalkylidene Synthesis

Studies on the synthesis, stability and conformation of 2-sulfonyl-oxetane fragments

Regio- and stereospecific synthesis of vinyl halides via carbozincation of acetylenic sulfones followed by halogenation

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