2003-82-9Relevant articles and documents
The Hexadehydro-Diels-Alder Cycloisomerization Reaction Proceeds by a Stepwise Mechanism
Wang, Tao,Niu, Dawen,Hoye, Thomas R.
, p. 7832 - 7835 (2016)
We report here experiments showing that the hexadehydro-Diels-Alder (HDDA) cycloisomerization reaction proceeds in a stepwise manner - i.e., via a diradical intermediate. Judicious use of substituent effects was decisive. We prepared (i) a series of triyn
Practical and safe procedures for the preparation of the lower homologues of bromoacetylene
Brandsma,Verkruijsse
, p. 984 - 985 (1990)
The lower homologues of bromoacetylene, from 1-bromopropyne to 1-bromo-1-hexyne, have been prepared in excellent yield by stirring the alkyne (in the cases of 1-propyne and 1-butyne a dilute solution in high-boiling petroleum ether) with a very concentrated aqueous solution of potassium hypobromite and potassium hydroxide.
Reactions of HDDA-Derived Benzynes with Sulfides: Mechanism, Modes, and Three-Component Reactions
Chen, Junhua,Palani, Vignesh,Hoye, Thomas R.
supporting information, p. 4318 - 4321 (2016/05/09)
We report here reactions of alkyl sulfides with benzynes thermally generated by the hexadehydro-Diels-Alder (HDDA) cycloisomerization. The initially produced 1,3-betaine (o-sulfonium/aryl carbanion) undergoes intramolecular proton transfer to generate a more stable S-aryl sulfur ylide. This can react in various manners, including engaging weak acids (HA) in the reaction medium. This can produce transient ion pairs ArSR2+A- that proceed to the products ArSR + RA. When cyclic sulfides are used, A- opens the ring and is incorporated into the product, an outcome that constitutes a versatile, three-component coupling process.