130700-02-6Relevant articles and documents
Acetyl chloride-ethanol brings about a remarkably efficient conversion of allyl acetates into allyl chlorides
Yadav, Veejendra K.,Ganesh Babu
, p. 9111 - 9116 (2003)
AcCl-EtOH transforms primary and secondary allyl acetates into allyl chlorides that retain the olefinic bond in the more stable position. Whereas secondary allyl alcohols also react with almost the same efficacy as the acetates, the reactions of primary allyl alcohols that possess 1, 2-disubstituted alkenes are very slow. The products are isolated in high state of purity simply by removal of the volatiles.
Stereodivergence in the Ireland-Claisen Rearrangement of α-Alkoxy Esters
Podunavac, Ma?a,Lacharity, Jacob J.,Jones, Kerry E.,Zakarian, Armen
supporting information, p. 4867 - 4870 (2018/08/24)
A systematic investigation into the Ireland-Claisen rearrangement of α-alkoxy esters is reported. In all cases, the use of KN(SiMe3)2 in toluene gave rearrangement products corresponding to a Z-enolate intermediate with excellent diastereoselectivity, presumably because of chelation control. On the other hand, chelation-controlled enolate formation could be overcome for most substrates through the use of lithium diisopropylamide (LDA) in tetrahydrofuran (THF).
1,n-rearrangement of allylic alcohols promoted by hot water: Application to the synthesis of navenone B, a polyene natural product
Li, Pei-Fang,Wang, Heng-Lu,Qu, Jin
, p. 3955 - 3962 (2014/05/20)
It was reported for the first time that hot water as a mildly acidic catalyst efficiently promoted 1,n-rearrangement (n = 3, 5, 7, 9) of allylic alcohols. In some cases, the rearrangement reactions joined isolated C-C double or triple bonds to generate conjugated polyene or enyne structure motifs. We used the 1,3-rearrangement reaction of an allylic alcohol in hot water as part of an attractive new strategy for construction of the polyene natural product navenone B by iterative use of a Grignard reaction, a 1,3-rearrangement of the resulting allylic alcohol, and subsequent oxidation of the rearranged product.
Copper-catalyzed enantioselective 1,4-addition to α,β- unsaturated aldehydes
Palais, Laetitia,Babel, Lucille,Quintard, Adrien,Belot, Sebastien,Alexakis, Alexandre
supporting information; experimental part, p. 1988 - 1991 (2010/07/10)
Figure presented The first asymmetric Cu-catalyzed conjugate addition of dialkylzinc zinc reagents to a large scope of enals in presence of phosphoramidite, SimplePhos, or (R)-BINAP ligands with enantiomeric excesses up to 90% is reported. Moreover, ACA of Grignard reagents afforded moderate to good 1,4-regioselectivities with enantioselectivities up to 90%.
Catalyst versus substrate induced selectivity: Kinetic resolution by palladacycle catalyzed allylic imidate rearrangements
Peters, Rene,Xin, Zhuo-Qun,Maier, Frank
supporting information; experimental part, p. 1770 - 1774 (2011/03/23)
Making chairs: A kinetic resolution of allylic imidates by planar chiral palladacycles is described which is the result of high face selectivity for olefin coordination to the catalyst and inherent substrate selectivity. These studies confirm that planar chiral palladacycles mainly operate via (half)chair-like transition states/intermediates.
Enantioselective, organocatalytic reduction of ketones using bifunctional thiourea-amine catalysts
Li, De Run,He, Anyu,Falck
supporting information; body text, p. 1756 - 1759 (2010/10/04)
Prochiral ketones are reduced to enantioenriched, secondary alcohols using catecholborane and a family of air-stable, bifunctional thiourea-amine organocatalysts. Asymmetric induction is proposed to arise from the in situ complexation between the borane and chiral thiourea-amine organocatalyst resulting in a stereochemically biased boronate-amine complex. The hydride in the complex is endowed with enhanced nucleophilicity while the thiourea concomitantly embraces and activates the carbonyl.
On the utility of α-heteroatom substituted orthoesters in the Johnson Claisen rearrangement
Elworthy, Todd R.,Morgans Jr., David J.,Palmer, Wylie S.,Repke, David B.,Smith, David B.,Waltos, Ann Marie
, p. 4951 - 4954 (2007/10/02)
α-Heteroatom substituted orthoesters were prepared and found to undergo the Johnson Claisen rearrangement with a variety of allylic alcohols giving γ,δ-unsaturated α-heteroatom substituted esters in fair to excellent yields. The diastereoselectivity of the process was examined.
Palladium-Catalyzed Cross-Coupling of Aryl Halides and Olefinic Epoxides via Palladium Migration
Larock, Richard C.,Leung, Wai-Yee
, p. 6244 - 6245 (2007/10/02)
The palladium-catalyzed cross-coupling of aryl halides and olefinic epoxides bearing one to ten carbons between the two functional groups afford good yields of arylated allylic alcohols by a palladium migration process.
