By Min Shi, Feijun Wang, Mei-Xin Zhao, Yin Wei, James J Spivey
Read Online or Download The Chemistry of the Morita-Baylis-Hillman Reaction PDF
Similar chemistry books
This quantity features a variety of subject matters similar to the activation and manipulation of pyrroles, the synthesis of annelated pyrroles utilizing acylation reactions and the synthesis of kainoids, a kinfolk of hugely biologically lively nitrogen heterocycles.
Content material: A century of polymer technological know-how and know-how / Herman F. Mark -- advent to polymer technological know-how and expertise / Charles E. Carraher, Jr. and Raymond B. Seymour -- Anionic polymerization / Maurice Morton -- Coordinated anionic polymerization and polymerization mechanisms / Frederick J. Karol -- fresh advancements in cationic polymerization / Virgil Percec -- Emulsion polymerization / Gary W.
- Potential Energy Surfaces: Proceedings of the Mariapfarr Workshop in Theoretical Chemistry
- Chocolate Science and Technology
- Advances in Heterocyclic Chemistry, Vol. 96
- The General X-Radiation from Mercury Vapor
- Topics in Stereochemistry, Volume 15
Additional resources for The Chemistry of the Morita-Baylis-Hillman Reaction
However, this hurdle has been surmounted by selection of appropriate reaction conditions. 10 It is also the exclusive path in the attempted addition of 2-pyridinecarboxaldehyde47 and a-diketones57 to acrolein. 48b More reactive electrophiles, including halo ketones,58 ﬂuorocarbonyls59 and activated imines,60 all reacted very rapidly with acrolein. 63 Using DMAP as catalyst, normal MBH adducts 69 were formed exclusively. 32), but for EVK, only the normal MBH adduct 69 was obtained. 33). 33). For aryl vinyl ketones, probably due to their rapid dimerization in the presence of DABCO, there is only one example of an MBH reaction, between phenyl vinyl ketone (PVK) and propionaldehyde catalyzed by rhodium or ruthenium complexes,62c providing the corresponding adduct 74, along with PVK dimer 75.
In contrast to the readiness of 162 to undergo the MBH reaction with acrolein and acrylonirile, all attempts to conduct an MBH reaction with 3,3,6,6-tetramethylcycohexane-1,2-dione (164), under similar conditions, met with failure. This result may be attributed to both greater steric inhibition of nucleophilic attack at the carbonyl group of 164 and the lack of enhanced reactivity associated with ‘‘eclipsing’’ the two carbonyl groups (as in 162). Norbornane-2,3-dione (165), an apparently logical candidate for testing, was reported to be unstable,143 which undoubtedly contributed to the unsatisfactory results obtained on attempting the MBH rection with acrylonitrile (8% yield of adduct).
Among the various catalysts screened, DABCO proved to be the best; DBU was too basic and led to polymerization. 41),88 but only one example of this class of compounds has been reported. 89 It was found that diethyl vinylphosphonate can be coupled with various aliphatic aldehydes in the presence of DABCO to give moderate to high yields of the corresponding a-hydroxyalkyl phosphonates 85. 42). 2 S Me 94 O SEt n n = 1, 2 90 1 O N O CO2Et R NH Me Me OH 95 Examples of novel activated alkenes. O O O O R O 91 O 92 28 Chapter 1 94 95 92, sugar derived chiral-activated alkenes 93, a-oxo ketene dithioacetals 9496 and p-methylquinols 95,97 for the synthesis of diverse products via MBH reaction with aldehydes or other electrophiles in the presence of tertiary amine or TiCl4 catalyst.
The Chemistry of the Morita-Baylis-Hillman Reaction by Min Shi, Feijun Wang, Mei-Xin Zhao, Yin Wei, James J Spivey