154659-34-4Relevant academic research and scientific papers
Regioselective radical bromoallylation of allenes leading to 2-bromo-substituted 1,5-dienes
Kippo, Takashi,Fukuyama, Takahide,Ryu, Ilhyong
, p. 3864 - 3867 (2011/09/15)
The regioselective radical bromoallylation of allenes proceeded efficiently in the presence of AIBN as a radical initiator to give 2-bromo-substituted 1,5-dienes in excellent yields. The addition of a bromine radical took place regioselectively onto the central carbon of allenes generating a stable allyl radical, which underwent addition/β-fragmentation reactions with allylbromides. The products could be further functionalized by Pd-catalyzed coupling reactions.
Aza cope rearrangement of propargyl enammonium cations catalyzed by a self-assembled "nanozyme"
Hastings, Courtney J.,Fiedler, Dorothea,Bergman, Robert G.,Raymond, Kenneth N.
supporting information; experimental part, p. 10977 - 10983 (2009/02/05)
The tetrahedral assembly [Ga4L6]12- [L = N,N-bis(2,3-dihydroxybenzoyl)-1,5-diaminonaphthalene) encapsulates a variety of cations, including propargyl enammonium cations capable of undergoing the aza Cope rearrangement. For propargyl enammonium substrates that are encapsulated in the [Ga4L6]12- assembly, rate accelerations by factors of up to 184 compared with the background reaction rate were observed. After rearrangement, the product iminium ion is released into solution and hydrolyzed, allowing for catalytic turnover. The activation parameters for the catalyzed and uncatalyzed reaction were determined, revealing that a decrease in the entropy of activation is responsible for the observed rate enhancements. The catalyzed reaction exhibits saturation kinetics: the rate data obeyed the Michaelis-Menten model of enzyme kinetics, and competitive inhibition using a nonreactive guest was demonstrated.
Nematic tolanes and acetylenes
Skelton, Graham W.,Dong, Dewen,Tuffin, Rachel P.,Kelly, Stephen M.
, p. 450 - 457 (2007/10/03)
The first liquid crystals incorporating a non-conjugated carbon-carbon triple bond in the terminal chain to exhibit a nematic phase above the melting point are reported. A variety of compounds incorporating a carbon-carbon triple bond in the terminal chain or between two phenyl rings have been synthesised as part of an investigation of the effects of the shape, conformation and rigidity of the terminal chains of liquid crystals on their mesophase behaviour. A series of related tolanes incorporating an alkenyloxy chain with an additional carbon-carbon double bond or a simple alkoxy chain as a terminal substituent also were prepared for comparison purposes.
