Unknown

Dataset Information

0

Gold(I)-Catalyzed Haloalkynylation of Aryl Alkynes: Two Pathways, One Goal.


ABSTRACT: Haloalkynylation reactions provide an efficient method for the simultaneous introduction of a halogen atom and an acetylenic unit. For the first time, we report a gold(I)-catalyzed haloalkynylation of aryl alkynes that delivers exclusively the cis addition product. This method enables the simple synthesis of conjugated and halogenated enynes in yields of up to 90?%. Notably, quantum chemical calculations reveal an exceptional interplay between the place of the attack at the chloroacetylene: No matter which C-C bond is formed, the same enyne product is always formed. This is only possible through rearrangement of the corresponding skeleton. Hereby, one reaction pathway proceeds via a chloronium ion with a subsequent aryl shift; in the second case the corresponding vinyl cation is stabilized by a 1,3-chlorine shift. 13 C-labeling experiments confirmed that the reaction proceeds through both reaction pathways.

SUBMITTER: Kreuzahler M 

PROVIDER: S-EPMC7318269 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

altmetric image

Publications

Gold(I)-Catalyzed Haloalkynylation of Aryl Alkynes: Two Pathways, One Goal.

Kreuzahler Mathis M   Haberhauer Gebhard G  

Angewandte Chemie (International ed. in English) 20200406 24


Haloalkynylation reactions provide an efficient method for the simultaneous introduction of a halogen atom and an acetylenic unit. For the first time, we report a gold(I)-catalyzed haloalkynylation of aryl alkynes that delivers exclusively the cis addition product. This method enables the simple synthesis of conjugated and halogenated enynes in yields of up to 90 %. Notably, quantum chemical calculations reveal an exceptional interplay between the place of the attack at the chloroacetylene: No m  ...[more]

Similar Datasets

| S-EPMC7181282 | biostudies-literature
| S-EPMC3795527 | biostudies-literature
| S-EPMC8611791 | biostudies-literature
| S-EPMC3419542 | biostudies-literature
| S-EPMC5745073 | biostudies-literature
| S-EPMC4446700 | biostudies-literature
| S-EPMC5634393 | biostudies-literature
| S-EPMC6430632 | biostudies-literature
| S-EPMC6781487 | biostudies-literature
| S-EPMC2569199 | biostudies-literature