105595-77-5Relevant academic research and scientific papers
Short synthesis of chiral 4-substituted (S)-imidazolinium salts bearing sulfonates and their use in γ-selective reactions of allylic halides with grignard reagents
Latham, Christopher M.,Blake, Alexander J.,Lewis, William,Lawrence, Matthew,Woodward, Simon
, p. 699 - 707 (2012/03/11)
A one-pot reaction of Boc-protected amino alcohols and 2-sulfobenzoic anhydride followed by the addition of a wide variety of primary amines has allowed rapid access to diverse libraries of amidosulfonates 1,2-C 6H4(SO3su
γ-Selective cross-coupling of allylic silanolate salts with aromatic bromides using trialkylphosphonium tetrafluoroborate salts prepared directly from phosphine?borane adducts
Denmark, Scott E.,Werner, Nathan S.
supporting information; experimental part, p. 4596 - 4599 (2011/10/12)
The γ-selective, palladium-catalyzed cross-coupling of sodium (Z)-2-butenyldiethylsilanolate with a variety of aromatic bromides is reported. The protocol provides high yields (73-94%) and site selectivity (γ/α, 25:1 → > 99:1) in the coupling of electron-
Cross-coupling of aromatic bromides with allylic silanolate salts
Denmark, Scott E.,Werner, Nathan S.
supporting information; experimental part, p. 16382 - 16393 (2009/05/08)
The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85°C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (γ-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher γ-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial γ-transmetalation followed by direct reductive elimination or σ-π isomerization can rationalize all of the observed trends.
γ-selective cross-coupling of potassium allyltrifluoroborates with aryl and 1-alkenyl bromides catalyzed by a Pd(OAc)2/D-t-BPF complex
Yamamoto, Yasunori,Takada, Shingo,Miyaura, Norio
, p. 704 - 705 (2007/10/03)
Cross-coupling reactions of [RCH=CHCH2BF3]K with aryl or 1-alkenyl bromides occurred at the γ-carbon of an allylborane moiety with perfect regioselectivities (>99%) in the presence of a palladium/D-t-BPF complex and K2COs
