6363-21-9Relevant academic research and scientific papers
Enantioselective 1,4-conjugate addition of diethylzinc to (E)-alkenyl aryl ketones catalysed by Cu/DiPPAM complex
Magrez, Magaly,Wencel-Delord, Joanna,Crévisy, Christophe,Mauduit, Marc
experimental part, p. 3507 - 3511 (2012/06/15)
We report here the use of the DiPPAM-L1 ligand for copper-catalysed asymmetric conjugate addition (ACA) of diethylzinc to various (E)-alkenyl aryl ketones where the aryl ring is either a phenyl group substituted by nitro, chloro or methoxy groups or not s
Templation of the excited-state chemistry of α-(n-alkyl) dibenzyl ketones: how guest packing within a nanoscale supramolecular capsule influences photochemistry
Gibb, Corinne L. D.,Sundaresan, Arun Kumar,Ramamurthy,Gibb, Bruce C.
, p. 4069 - 4080 (2008/12/20)
Excited-state behavior of eight α-alkyl dibenzyl ketones (alkyl = CH3 through n-C8H17) that are capable of undergoing type II and/or type I photoreactions has been explored in isotropic solution and within a water-soluble capsule. The study consisted of two parts: photochemistry that explored the excited-state chemistry and an NMR analysis that revealed the packing of each guest within the capsule. The NMR data (COSY, NOESY, and TOCSY experiments) revealed that ternary complexes between α-alkyl dibenzyl ketones and the capsule formed by two cavitands are kinetically stable, and the guests fall into three packing motifs modulated by the length of the α-alkyl chain. In essence, the host is acting as an external template to promote the formation of distinct guest conformers. The major products from all eight guests upon irradiation either in hexane or in buffer solution resulted from the well-known Norrish type I reaction. However, within the capsule the excited-state chemistry of the eight ketones was dependent on the alkyl chain length. The first group consisted of α-hexyl, α-heptyl, and α-octyl dibenzyl ketones that yielded large amounts of Norrish type II products within the host, while in solution the major products were from Norrish type I reaction. The second group consists of α-butyl and α-pentyl dibenzyl ketones that yield equimolar amounts of two rearranged starting ketones within the capsule (combined yield of ca 60%), while in solution no such products were formed. The third group consisted of α-methyl, α-ethyl, and α-propyl dibenzyl ketones that within the capsule yielded only one (not two) rearranged starting ketone in larger amounts (21-35%) while in solution no rearrangement product was obtained. Variation in the photochemistry of the guest within the capsule, with respect to the α-alkyl chain length of the guest, highlights the importance of how a small variation in supramolecular structure can influence the selectivity within a confined nanoscale reactor.
Biphenol-based phosphoramidite ligands for the enantioselective copper-catalyzed conjugate addition of diethylzinc
Alexakis, Alexandre,Polet, Damien,Rosset, Stephane,March, Sebastien
, p. 5660 - 5667 (2007/10/03)
Phosphoramidite ligands, based on ortho-substituted biphenols and a chiral amine, induce high enantioselectivities (ee's up to 99%) in the copper-catalyzed conjugate addition of dialkylzinc reagents to a variety of Michael acceptors. Particularly, the best reported ee's were obtained for acyclic nitroolefins.
Regioselective Allylation of Ketenes Promoted by SmI2
Miyoshi, Norikazu,Takeuchi, Seiji,Ohgo, Yoshiaki
, p. 445 - 451 (2007/10/02)
Ketenes react with various allylic halides mediated by 2 equiv. samarium(II) diiodide (SmI2) to the ketenes to afford allylated ketones in good yields.In the reaction with γ-substituted allylic halides, the regioselectivity is influenced by the olefinic geometry of allylic halides.By using γ-substituted (E)-allylic halides, the allylation proceeds on the less hindered site (α-position) of allylic groups predominantly and the tendency was enhanced by the addition of HMPA.
Asymmetric Synthesis of Ketones by SmI2-Mediated Allylation or Benzylation of Ketenes Followed by Enantioselective Protonation
Takeuchi, Seiji,Miyoshi, Norikazu,Ohgo, Yoshiaki
, p. 551 - 554 (2007/10/02)
SmI2-mediated allylation or benzylation of alkylarylketenes followed by enantioselective protonation with α,α'-di-o-xylenedioxide gave the corresponding ketones in 61-91percentee.
