Cyano-acroleine

Predict the regioselectivity in the Diels-Alder reactions of acrolein and N-acetyl-2-cyano-4-phenyl-l-azabutadiene with 1-hexene, styrene, ethyl vinyl ether and methyl acrylate. The FOs of the azadiene are given below the others may be found in the Appendix. 

Asymmetric Michael additionA catalyst prepared from RhH(CO)[P(C,H<,)2l2 and TRAP can effect asymmetric addition of a-cyano carboxylates to vinyl ketones or acrolein. Note that isopropyl esters show the highest selectivity. 

Substituents such as carbonyl and cyano are electron-withdrawing and activate the dienophile toward cycloaddition. The electron-attracting properties of these groups arise from bond dipoles, which place a partial positive charge on the carbonyl or cyano carbon (see Section 1.5). Acrolein has one electron-withdrawing group attached to its dienophilic double bond. Diethyl fumarate and maleic anhydride, the most reactive and synthetically useful dienophiles you will encounter in this section, both have two. 

Tryptophan is obtained industrially by a variation of the Fischer indole synthesis. Addition of hydrogen cyanide to acrolein gives 3-cyano-propanal which is converted to hydantoin through a Bucherer reaction. The nitrile group is then... 

Addition of keten to 3-dialkylaminovinylthiones provides a route to 4,6-diaryl- or 6-aryl-2H-thiopyran-2-ones, whilst 5,6-diaryl-3-cyano-derivatives can be prepared from (3-mercapto- or 3-chloro-acroleins (22 R = SH or Cl). Full details have been published of the formation of 2H-thiopyran-2-thiones in condensation reactions between 1,2-dithiolium salts and aroyldithioacetic esters. ... 

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