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Understanding the highly regioselective cyanothiolation of 1-alkynes catalyzed by palladium phosphine complexes
Citation
Zheng, W and Ariafard, A and Lin, Z, Understanding the highly regioselective cyanothiolation of 1-alkynes catalyzed by palladium phosphine complexes, Organometallics, 27, (2) pp. 246-253. ISSN 0276-7333 (2008) [Refereed Article]
Copyright Statement
Copyright 2008 American Chemical Society
Abstract
A computational study with the Becke3LYP DFT functional was carried out on the palladium-catalyzed
regioselective cyanothiolation of 1-alkynes with thiocyanates. The full catalytic cycle was computed,
starting from the oxidative addition and finishing with the reductive elimination. The two most important
issues, namely, the regioselective bond cleavage of thiocyanates and the nature of insertion of 1-alkynes
into a Pd-S bond, are discussed. The calculations indicate that the sulfur-cyano (PhS-CN) bond cleavage
on Pd(0) is kinetically and thermodynamiclly more favorable than the carbon-sulfur (Ph-SCN) bond
cleavage. The kinetic preference of 1,2-insertion over 2,1-insertion in the alkyne insertion step leads to
the cyanothiolation products with the SPh group attached to the substituted carbon atom of 1-alkynes.
Item Details
| Item Type: | Refereed Article |
|---|---|
| Research Division: | Chemical Sciences |
| Research Group: | Other Chemical Sciences |
| Research Field: | Organometallic Chemistry |
| Objective Division: | Expanding Knowledge |
| Objective Group: | Expanding Knowledge |
| Objective Field: | Expanding Knowledge in the Chemical Sciences |
| Author: | Ariafard, A (Associate Professor Alireza Ariafard) |
| ID Code: | 91070 |
| Year Published: | 2008 |
| Web of Science® Times Cited: | 36 |
| Deposited By: | Chemistry |
| Deposited On: | 2014-05-07 |
| Last Modified: | 2014-06-10 |
| Downloads: | 0 |
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