66478-41-9Relevant academic research and scientific papers
Synthesis of α,β-unsaturated aldehydes and nitriles via cross-metathesis reactions using Grubbs' catalysts
Rountree, Sandra M.,Taylor, Sarah F.R.,Hardacre, Christopher,Lagunas, M. Cristina,Davey, Paul N.
, p. 94 - 104 (2015/09/28)
A series of α,β-unsaturated aldehydes and nitriles of significant interest in the fragrance industry have been prepared using Grubbs' catalysts in cross-metathesis reactions of electron-deficient olefins (i.e., acrolein, crotonaldehyde, methacrolein, and acrylonitrile) with various 1-alkenes, including 1-decene, 1-octene, 1-hexene and 2-allyloxy-6-methylheptane. The latter is of particular interest, as it has not previously being used as a substrate in cross-metathesis reactions and allows access to valuable intermediates for the synthesis of new fragrances. Most reactions gave good selectivity of the desired CM product (≥90%). Detailed optimisation and mechanistic studies have been performed on the cross-metathesis of acrolein with 1-decene. Recycling of the catalyst has been attempted using ionic liquids.
ALPHA, BETA, UNSATURATED NITRILES AS FRAGRANCES
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Page/Page column 5, (2008/06/13)
The use of short chain α,β-unsaturated nitriles as flavour and fragrance ingredient and flavour and fragrance applications comprising them.
Highly active phosphine-free carbene ruthenium catalyst for cross-metathesis of acrylonitrile with functionalized olefins
Bai, Chen-Xi,Zhang, Wen-Zhen,He, Ren,Lu, Xiao-Bing,Zhang, Zhi-Qiang
, p. 7225 - 7228 (2007/10/03)
The carbene ruthenium complex [1,3-bis(2,6-dimethylphenyl)-4,5- dihydroimidazol-2-ylidene](C5H5N)2(Cl) 2RuCHPh (8) was prepared by the reaction of [1,3-bis (2,6-dimethylphenyl)-4,5-dihydroimidazol-2-ylidene](PPh3)(Cl) 2RuCHPh (7) with pyridine and used as a highly effective catalyst for the cross-metathesis of acrylonitrile with various functionalized olefins.
The Cyanation of Vinyl Halides with Alkali Cyanides Catalyzed by Nickel(0)-Phosphine Complexes Generated In Situ: Synthetic and Stereochemical Aspects
Sakakibara, Yasumasa,Enami, Hiroji,Ogawa, Hiroshi,Fujimoto, Shinpei,Kato, Hiroyuki,et al.
, p. 3137 - 3144 (2007/10/03)
The cyanation of β-bromostyrenes catalyzed by Ni(PPh3)n, which was generated in situ from NiBr2(PPh3)2-Zn-PPh3 (Ni:Zn:P=1:3:2 molar ratio), was at first examined with various MCN (M=K, Na)-dipolar aprotic solvent systems by several procedures.The presence of excess cyanide ion inhibited the reaction.However, when the KCN-DMF system with some intermediate cyanide solubility was used, the nitriles were obtained in high yields and high stereoselectivity at 50 deg C by almost all of the procedures attempted.On the contrary, the KCN-HMPA and KCN-MeCN systems with cyanide solubilities accelerated the coupling of the halides to inhibit the cyanation, and in general the NaCN-DMF and NaCN-HMPA systems with high cyanide solubilities needed to reduce Ni(II) before adding MCN in order to make the catalytic reaction start.Vinyl halides such as 1- and 2-halo (Cl, Br)-1-alkenes, 2-bromo-2-butenes, 3-bromo-3-hexenes, and 1-chlorocyclohexene were also cyanated using suitable procedures and MCN-solvent systems to give the corresponding nitriles in high yields and fair-to-good stereoselectivities.However, with (Z)-2-ethoxy-1-bromoethene the (E)-nitrile, though its selectivity markedly varied with the reaction temperature, was obtained as the main product.The cyanation of ethyl (Z)-β-bromoacrylate and ethyl α-bromoacrylate was unsuccessful due to polymerization.
THE CYANATION OF VINYL HALIDES CATALYZED BY NICKEL(0) COMPLEX GENERATED IN SITU
Sakakibara, Yasumasa,Yadani, Nobuichi,Ibuki, Ichiro,Sakai, Mutsuji,Uchino, Norito
, p. 1565 - 1566 (2007/10/02)
Nickel(0) species generated in situ from NiBr2(PPh3)2-Zn-PPh3 catalyzed the formation of unsaturated nitriles from vinyl halides and potassium cyanide.The reaction proceeded under very mild conditions and was stereoselective.
