30567-26-1Relevant articles and documents
Efficient Access to All-Carbon Quaternary and Tertiary α-Functionalized Homoallyl-type Aldehydes from Ketones
Pace, Vittorio,Castoldi, Laura,Mazzeo, Eugenia,Rui, Marta,Langer, Thierry,Holzer, Wolfgang
supporting information, p. 12677 - 12682 (2017/09/08)
β,γ-Unsaturated aldehydes with all-carbon quaternary or tertiary α-centers were rapidly assembled from ketones through a unique synthetic operation consisting of 1) C1 homologation, 2) Lewis acid mediated epoxide–aldehyde isomerization, and 3) electrophilic trapping. The synthetic equivalence of a vinyl oxirane and a β,γ-unsaturated aldehyde is the key concept of this previously undisclosed tactic. Mechanistic studies and labeling experiments suggest that an aldehyde enolate is a crucial intermediate. The homologating carbenoid formation plays a critical role in determining the chemoselectivity.
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.
Regioselective hydroformylation of allylic alcohols
Lightburn, Thomas E.,De Paolis, Omar A.,Cheng, Ka H.,Tan, Kian L.
, p. 2686 - 2689 (2011/06/28)
A highly regioselective hydroformylation of allylic alcohols is reported toward the synthesis of β-hydroxy-acid and aldehyde products. The selectivity is achieved through the use of a ligand that reversibly binds to alcohols in situ, allowing for a directed hydroformylation to occur. The application to trisubstituted olefins was also demonstrated, which yields a single diastereomer product consistent with a stereospecific addition of CO and hydrogen.
A general route to α-alkyl (E)-α,β-unsaturated aldehydes
Lahmar, Nour,Aatar, Jamaa,Ayed, Ta?cir Ben,Amri, Hassen,Bellassoued, Moncef
, p. 3018 - 3026 (2007/10/03)
Bis(trimethylsilyl)-tert-butylaldimines 3 react with aldehydes in the presence of zinc bromide at room temperature to give, after hydrolysis, the desired α-alkyl α,β-ethylenic aldehydes in good yield and with very high E stereoselectivity. The reaction was believed to proceed via the α-silyl β-siloxyimines 4.
A new route to α,β-unsaturated aldehydes using the condensation of trimethylsilyl β-trimethylsilyl enol ethers with aldehydes
Duhamel, Lucette
, p. 7745 - 7748 (2007/10/02)
β-Trimethylsilyl enol ethers 1 (Z) obtained from β-bromoenolethers 2 were condensed with aliphatic and aromatic aldehydes in the presence of a catalytic quantity of trimethylsilyl triflate leading to ethylenic aldehydes 3 (E) with good yields (79-90%).
Preparation of 3-cyano-2-alkylalkanals
-
, (2008/06/13)
3-Cyanoaldehydes of the formula I STR1 where R1 and R2 are each C1 -C6 -alkyl and R3 is hydrogen or C1 -C3 -alkyl, are prepared by a process wherein an aldehyde of the formula II STR2 is reacted with anhydrous hydrocyanic acid in the presence of a basic catalyst, in a solvent.
Synthesis of α,β-Unsaturated Carbonyl Compounds by Successive Rearrangement and Peterson Olefination of β'-Hydroxy-α,β-epoxysilanes
Sato, Fumie,Tanaka, Youichi,Kanbara, Hiroshi
, p. 1024 - 1025 (2007/10/02)
The reaction of β'-hydroxy-α,β-epoxysilanes with boron trifluoride-diethyl ether results in rearrangement of the epoxysilane skeleton followed by Peterson olefination, leading to α,β-unsaturated carbonyl compounds.
