144102-19-2Relevant academic research and scientific papers
The hydroboration of propargyl chloride: A flexible one-pot three-component process easily directed towards the synthesis of (E)-homoallylic alcohols or anti-homoallylic alcohols
Lombardo, Marco,Morganti, Stefano,Trombini, Claudio
, p. 601 - 604 (2007/10/03)
The hydroboration of propargyl chloride by means of a dialkylborane affords 3-chloro-propenyl boranes 6 which, in the presence of a quaternary ammonium chloride, rearrange into allylic boranes 9 and 10, precursors of (E)-homoallylic alcohols 7 or anti-homoallylic alcohols 5, respectively. Synthetic protocols for the selective generation of 5 and 7 were developed.
Ultrasound-promoted Carbonyl Allylation by Allylic Alcohols with Palladium-Tin Dichloride in Nonpolar Solvents: Inversed Regiocontrol of Carbonyl Allylation in Polar Solvents
Masuyama, Yoshiro,Hayakawa, Akiko,Kurusu, Yasuhiko
, p. 1102 - 1103 (2007/10/02)
Heterogeneous carbonyl allylation by γ-substituted allylic alcohols with Pd-SnCl2 in nonpolar solvent such as diethyl ether was promoted by ultrasound to cause α-addition, with a regioselectivity which is the inverse of that in homogeneous carbonyl allylation in polar solvents such as dimethylformamide, 1,3-dimethylimidazolidin-2-one and tetrahydrofuran-H2O.
Palladium-catalyzed carbonyl allylation by allylic alcohols with SnCl2
Takahara, Jun P.,Masuyama, Yoshiro,Kurusu, Yasuhiko
, p. 2577 - 2586 (2007/10/02)
Allylic alcohols can be applied to carbonyl allylation via the formation of π-allylpalladium complexes, using palladium as catalyst and SnCl2 as a reducing agent. This reaction has chemoselectivity: The reactivity order of allylating agents is allylic carbonate > allylic alcohol > allylic acetate, and that of carbonyl compounds is aldehyde > ketone. High regioselcction was observed in polar solvents such as DMF, DMI, and DMSO; carbonyl compounds apparently attacked the more substituted allylic position of π-allylpalladium complexes to afford only one regioisomer. Diastereocontrol in the carbonyl allylation of aromatic aldehydes by (E)-2-butenol was achieved by the choice of polar solvents; use of DMSO at 25 °C led to syn selection, while anti selection was found at -10 °C in THF. The addition of H2O in any solvent accelerated the carbonyl allylation and enhanced both regioselectivity and the diastereoselectivity. Anti selection in DMF, DMI, and THF-H2O can be explained by the chair form of the six-membered cyclic transition state, while syn selection in DMSO allows us to propose an acyclic antiperiplanar transition state. An NMR spectroscope investigation demonstrated that the actual allylating agent in dry medium was allyltrichlorotin: 1H, 13C, and 119Sn NMR spectra of the reaction of allyl alcohol with PdCl2(PhCN)2-SnCl2 in DMF-d7. corresponded to those of the reaction of allyl chloride with PdCl2(PhCN)2-SnCl2 in DMF-d7.
