99431-03-5Relevant academic research and scientific papers
Stereospecific, Nickel-Catalyzed Suzuki-Miyaura Cross-Coupling of Allylic Pivalates to Deliver Quaternary Stereocenters
Cobb, Kelsey M.,Rabb-Lynch, Javon M.,Hoerrner, Megan E.,Manders, Alex,Zhou, Qi,Watson, Mary P.
, p. 4355 - 4358 (2017)
Recognizing the importance of all-carbon, quaternary stereocenters in complex molecule synthesis, a stereospecific, nickel-catalyzed cross-coupling of allylic pivalates with arylboroxines to deliver products equipped with quaternary stereocenters and internal alkenes was developed. The enantioenriched allylic pivalate starting materials are readily prepared, and a variety of functional groups can be incorporated on both the allylic pivalate and the arylboroxine. Additional advantages include the use of a commercially available and air-stable Ni(II) salt and BISBI ligand, mild reaction conditions, and high yields and ee's. The observed stereoinversion of this reaction is consistent with an open transition state in the oxidative addition step.
Regioselective synthesis of β-fluoro-α,β-unsaturated ketones by the reaction of β-diketones with DFMBA
Sano, Keisuke,Fukuhara, Tsuyoshi,Hara, Shoji
experimental part, p. 708 - 713 (2010/04/05)
The deoxyfluorination reaction of β-diketones with N,N-diethyl-α,α-difluoro-m-methylbenzylamine (DFMBA) gave β-fluoro-α,β-unsaturated ketones in good yields. The reaction proceeded regioselectively, and only one regioisomer was obtained from the unsymmetr
A Stereoselective Synthesis of (E)-α,β-Unsaturated Ketones Involving the Reactions of Organocerium Reagents with Secondary β-Enamino Ketones
Bartoli, Giuseppe,Marcantoni, Enrico,Petrini, Marino,Sambri, Letizia
, p. 913 - 918 (2007/10/03)
Stereoselective construction of trisubstituted alkenes has wide applicability to the synthesis of many natural products.Specifically, β-disubstituted enones are important functionalized trisubstituted alkene targets.The reaction of organocerium reagents with secondary β-enamino ketones affords β-disubstituted α,β-unsaturated ketones in fairly good yields.This process shows considerable stereoselectivity, and α,β-unsaturated ketones of (E) configuration are predominantly observed.Organolithium-derived cerium reagents display better stereoselectivity than organomagnesium-based ones.The mechanism of the reaction varies with nitrogen substitution: N-phenyl groups give 1,2-addition products, whereas substitution products are observed with N-alkyl groups.When organocerium reagents were used with β-enamino ketones bearing secondary alkyl groups at the nitrogen atom, a lack of reactivity was observed. - Keywords: assymetric substitution; cerium reagents; enamino ketones; regioselectivity; synthetic methods
