77145-83-6Relevant academic research and scientific papers
Rhodium-catalyzed codimerization of n-butenes with allylic halides
Behr, Arno,Bayrak, Zeynep,Peitz, Stephan,Maschmeyer, Dietrich,Stochniol, Guido
, p. 68 - 71 (2014/04/03)
This paper describes the codimerization of n-butenes with allylic halides such as cinnamyl chloride and crotyl chloride. The highly active catalyst RhCl3·3H2O was investigated, resulting 70% yield of codimers with cinnamyl chloride and 1-butene. Furthermore, the reaction is dependent on the molar ratio of allylic chloride to RhCl3· 3H2O ratio, where a ratio of 75:1 is optimal at a catalyst concentration of 2 mol%. Additionally allylic compounds such as cinnamyl chloride lead to higher yields of the codimer than other short chained allylic chlorides. So the codimerization of an allylic compound with 1-butene represents a simple method to produce short chained dienes at very mild reaction conditions.
Integrated chemical process. One-pot preparation of olefins by alkylation and desulfonylation
Orita, Akihiro,Watanabe, Akihiro,Otera, Junzo
, p. 1025 - 1026 (2007/10/03)
Integration of alkylation of allylic sulfone and reductive desulfonylation under basic conditions effects one-pot synthesis of various olefins.
COPPER- AND NICKEL-CATALYSIS IN SN2'- AND SN2-REGIOSELECTIVE ALLYLATION OF ORGANOZINC REAGENTS
Sekiya, Kouichi,Nakamura, Eiichi
, p. 5155 - 5156 (2007/10/02)
Allylation of organozinc reagents in the presence of a copper catalyst takes place in a highly SN2'-selective manner, whereas that in the presence of a nickel catalyst occurs with excellent SN2-selectivity.
SPECIFIC ALLYLIC-ALLYLIC COUPLING PROCEDURES EFFECTED BY LIGAND-INDUCED ELIMINATION FROM DI(ALLYLIC)PALLADIUM SPECIES
Goliaszewski, Alan,Schwartz, Jeffrey
, p. 5779 - 5790 (2007/10/02)
Bis(allylic)palladium complexes can be induced to undergo reductive elimination by replacement of phosphine ligands in the system with ?-acidic ligands.The product 1,5-dienes, formed in high yield, are predominantly the 'head-to-head' coupled isomers.The bis(allylic)palladium intermediates may be formed by addition of an allylic Grignard or trialkyl(allylic)tin reagent to an(η3-allyl)palladium chloride complex, or by 1,3-diene condensation.The latter process leads to cyclodimerization, 'unusual' for palladium catalysed reactions.
Reaction Of Allylic Boron and Aluminium "Ate" Complexes with Organic Halides and Carbonyl Compounds. Trialkylboranes as Regio-, Stereo-, and Chemoselective Control Elements
Yamamoto, Yoshinori,Yatagai, Hidetaka,Maruyama, Kazuhiro
, p. 1969 - 1975 (2007/10/02)
Lithium allylic boron ate complexes, prepared by the addition of trilakylboranes to an ether solution of allylic lithium compounds, regioselectively react with allylic halides to produce head-to-tail 1,5-dienes (eq 1).The ate complexes are also prepared from the reaction of allylic boranes with alkyllithium derivatives.Magnesium or copper allylic boron ate complexes are less effective.Lithium crotyl boron ate complexes undergo a rapid reaction with aldehydes with good threoselectivity (eq 2).The selectivity is affected by the steric hindrance of trialkylboranes, as explained by the steric parameters of the 6-membered transition state.The ate complexes react with α,β-unsaturated ketones in a competitive manner of 1,2 and 1,4 addition, while they add to cinnamaldehyde exclusively in a 1,2 manner.The chemoselective aspects are only investigated. 1H and 13 C NMR spectra of lithium allylic boron ate complexes clearly indicate (i) the prevention of allylic rearrangement, (ii) the predominant trans geometry of the crotyl unit in comparison with the corresponding trivalent crotylboron, and (iii) the relative importance of ?-? conjugation between the double bond and the carbon-boron bond (eq 3).
