144061-75-6Relevant articles and documents
AN INVESTIGATION OF THE INFLUENCE OF HALOARENES AND HETARYLACETONITRILES ON THE COMPETITION BETWEEN POSSIBLE ARYNE ARYLATION AND TANDEM ADDITION-REARRANGEMENT PATHWAYS
Deshmukh, A. Rakeeb,Morgan, Matt,Tran, Long,Zhang, Hongming,Dutt, Mahesh,Biehl, Edward R.
, p. 1239 - 1249 (2007/10/02)
Attempts to extend the LDA-mediated 1-aminoisoquinoline arynic synthesis to 1,2-dibromo-3,4,5,6-tetramethylbenzene (1a) and the hetarylacetonitriles 2- (2a) and 3-pyridylacetonitrile (2b), 2- (2c) and 3-thiopheneacetonitrile (2d), and 2-benzimidizoylacetonitrile (2e) failed; only rearranged 2-hetarylmethyl-3,4,5,6-tetramethylbenzonitriles (3aa-3ae) were obtained.Additionally, the reaction of 1-chloro-2,5-dimethylbenzene (1b), 2-bromo-4-methylanisole (1c), bromobenzene (1d), 2-bromoanisole (1e), and 1-bromo-2,5-dimethoxybenzene (1f) with 2a-e gave rearranged nitriles (3) by the tandem addition-rearrangement aryne pathway and/or aryne arylated nitriles (4) by the aryne arylation pathway.By evaluating product 3:4 ratios from these reactions, an assessment of the influence of the nature of the haloarenes and hetarylacetonitriles on the competing tandem addition-rearrangement and aryne arylation pathways was made, which showed that the preference of the haloarenes for the rearrangement pathway to be 1a ca. 1b > 1c > 1d > 1e > 1f and that for the hetarylacetonitriles to be 2c ca. 2d > 2b > 2a > 2e.An explanation in terms of the influence of the haloarene substituents on the ring-closure step of the rearrangement pathway and the heterocyclic ring of the hetarylacetonitrile on the proton abstraction step of the alternate aryne arylation pathway is presented.
