501072-60-2Relevant academic research and scientific papers
Chiral propargyl alcohols via the enantioselective addition of terminal Di- and triynes to aldehydes
Graham, Erin R.,Tykwinski, Rik R.
, p. 6574 - 6583 (2011/10/05)
The enantioselective addition of di- and triynes to aldehydes is presented, including the first examples of an asymmetric triyne addition. Modification of the Carreira alkynylation protocol shows that addition of diynes and triynes to α-branched aldehydes can be complete in as little as 4 h, and these reactions give good yields and enantioselectivities (up to 98% ee) for di- and triynes tested (aryl, alkyl, and silyl). It is shown for two cases (20 and 24) that products of this asymmetric addition reaction can undergo further manipulation (desilylation and triazole formation) without affecting the enantiopurity.
Synthesis of unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes via alkylidene carbenoid rearrangements
Shi Shun, Annabelle L. K.,Chernick, Erin T.,Eisler, Sara,Tykwinski, Rik R.
, p. 1339 - 1347 (2007/10/03)
Unsymmetrically substituted 1,3-butadiynes and 1,3,5-hexatriynes are synthesized in four steps from commercially available aldehydes or carboxylic acids. The key step in this process involves a Fritsch-Buttenberg-Wiechell rearrangement, in which an alkylidene carbenoid intermediate subsequently rearranges to the desired polyyne. This rearrangement proceeds under mild conditions, and it is tolerant of a range of functionalities. In general, the procedurally facile formation of the dibromoolefinic precursors, in combination with the effectiveness of the rearrangement step, makes this procedure an attractive alternative to traditional methods for di- and triyne synthesis that utilize palladium or copper catalysis.
