71504-29-5Relevant academic research and scientific papers
Internal Lewis acid assisted benzoic acid catalysis
Auvil, Tyler J.,Mattson, Anita E.
supporting information; experimental part, p. 2173 - 2180 (2012/09/22)
Internal Lewis acid assisted benzoic acid derivatives are introduced as new low-molecular-weight single-hydrogen-bond donor catalysts for the activation of nitroalkenes. Selected 2-borylbenzoic acid derivatives gave good yields of products in the addition of indoles to nitroalkenes. Control experiments suggest that both the internal Lewis acid coordination and the carboxylic acid functionalities are critical to the optimal performance of these catalysts. Georg Thieme Verlag Stuttgart New York.
A flow microreactor system enables organolithium reactions without protecting alkoxycarbonyl groups
Nagaki, Aiichiro,Kim, Heejin,Moriwaki, Yuya,Matsuo, Chika,Yoshida, Jun-Ichi
supporting information; experimental part, p. 11167 - 11177 (2010/11/04)
A flow microreactor system consisting of micromixers and microtube reactors provides an effective tool for the generation and reactions of aryllithiums bearing an alkoxycarbonyl group at para-, meta-, and ortho-positions. Alkyl p- and m-lithiobenzoates were generated by the I/Li exchange reaction with PhLi. The Br/Li exchange reactions with sBuLi were unsuccessful. Subsequent reactions of the resulting aryllithiums with electrophiles gave the desired products in good yields. On the other hand, alkyl o-lithiobenzoates were successfully generated by the Br/ Li exchange reaction with sBuLi. Subsequent reactions with electrophiles gave the desired products in good yields.
Gold-catalyzed oxidative coupling reactions with aryltrimethylsilanes
Brenzovich Jr., William E.,Brazeau, Jean-Francois,Toste, F. Dean
supporting information; experimental part, p. 4728 - 4731 (2010/12/25)
During continuing studies with a novel oxidative gold oxyarylation reaction, arylsilanes were found to be competent coupling partners, providing further evidence for an intramolecular electrophilic aromatic substitution mechanism. While providing yields complementary to those of the previously described boronic acid methods, the use of trimethylsilanes reduces the observation of homocoupling byproducts and allows for facile intramolecular coupling reactions.
Aryllithium compounds bearing alkoxycarbonyl groups: Generation and reactions using a microflow system
Nagaki, Aiichiro,Kim, Heejin,Yoshida, Jun-Ichi
supporting information; experimental part, p. 7833 - 7836 (2009/04/10)
Go with the flow: An effective method for the generation and reaction of aryllithium compounds bearing an alkoxycarbonyl group is developed using microflow systems with very short residence times together with fast mixing and efficient temperature control. A wide range of alkoxycarbonyl groups including ethoxycarbonyl and methoxycarbonyl groups are tolerant of the microflow conditions. (Chemical Equation Presented)
Photochemical and acid-catalyzed rearrangements of 4-carbomethoxy-4-methyl-3-(trimethylsilyl)-2,5-cyclohexadien-1-one
Schultz, Arthur G.,Antoulinakis, Evan G.
, p. 4555 - 4559 (2007/10/03)
The synthesis of 4-carbomethoxy-4-methyl-3-(trimethylsilyl)-2,5-cyclohexadien-1-one (1) in 60% overall yield from benzaldehyde is described. Irradiation (366 nm) of 1 in benzene solution gave products of type A photorearrangement; e.g., diastereomers of the 4-(trimethylsilyl)- and 5-(trimethylsilyl)bicyclo[3.1.0]hex-3-en-2-ones 8 and 9. Bicyclohexenones 9a and 9b could not be isolated, but underwent acid-catalyzed protiodesilylative rearrangements on attempted chromatography (silica gel) to give a 1:1 mixture of (E)- and (Z)-4-(carbomethoxymethylmethylene)cyclopent-2-en-1-ones 12 and 13. Irradiation (366 nm) of either 12 or 13 resulted in photoisomerization to a photostationary state that was also a 1:1 mixture. Irradiation of 8a or 8b gave equivalent mixtures of phenols 14 and 15 by way of the type B oxyallyl zwitterion 17. The available experimental evidence suggests that both 9a and 9b undergo regiospecific photorearrangement to phenol 16 with no trace of 3-methyl-4-carbomethoxyphenol (19), the product of ipso substitution of the Me3Si group at C(4). Phenol 15 was isolated in 65% yield from the photoreaction of 1 in benzene with 20 equiv of CF3CO2H. The acid-catalyzed rearrangement of 1 to 3-carbomethoxy-4-methylphenol (21) occurs in 91% yield by way of CO2Me group rearrangement to C(3) to give the Me3Si-stabilized carbocation 23.
