- Catalytic Nucleophilic Allylation Driven by the Water-Gas Shift Reaction
-
The ruthenium-catalyzed allylation of aldehydes with allylic pro-nucleophiles has been demonstrated to be an efficient means to form carbon-carbon bonds under mild conditions. The evolution of this reaction from the initial serendipitous discovery to its general synthetic scope is detailed, highlighting the roles of water, CO, and amine in the generation of a more complete catalytic cycle. The use of unsymmetrical allylic pro-nucleophiles was shown to give preferential product formation through the modulation of reaction conditions. Both (E)-cinnamyl acetate and vinyl oxirane were efficiently used to form the anti-branched products (up to >20:1 anti/syn) and E-linear products (up to >20:1 E/Z) in high selectivity with aromatic, α,β-unsaturated, and aliphatic aldehydes, respectively. Attempts to render the reaction enantioselective are highlighted and include enantioenrichment of up to 75:25 for benzaldehyde.
- Denmark, Scott E.,Matesich, Zachery D.,Nguyen, Son T.,Milicevic Sephton, Selena
-
-
- Catalytic, nucleophilic allylation of aldehydes with allyl acetate
-
(Chemical Equation Presented) A new catalytic allylation of aldehydes has been developed that employs allyl acetate as the allylating reagent. Under catalysis by ruthenium trichloride (3 mol %) in the presence of carbon monoxide (30 psi), water (1.5 equiv), and Methylamine (0.1 equiv), a wide range of aromatic, olefinic, and aliphatic aldehydes are efficiently allylated under mild conditions (70 °C, 24-48 h). The stoichiometric byproducts of this reaction are carbon dioxide and acetic acid.
- Denmark, Scott E.,Nguyen, Son T.
-
supporting information; experimental part
p. 781 - 784
(2009/08/12)
-
- Pd-catalyzed nucleophilic allylic alkylation of aliphatic aldehydes by the use of allyl alcohols
-
Under catalysis of Pd(OAc)2-(P-n-Bu)3, Et 2Zn promotes a variety of allyl alcohols to undergo nucleophilic allylation of aliphatic aldehydes and ketones at room temperature and provides homoallyl alcohols in 60-90 and ca. 60% isolated yield, respectively. The reaction is irreversible and kinetically controlled, and unique regio- and stereoselectivities observed for the allylation with unsymmetrically substituted allyl alcohols are discussed.
- Kimura, Masanari,Shimizu, Masamichi,Tanaka, Shuji,Tamaru, Yoshinao
-
p. 3709 - 3718
(2007/10/03)
-