Fast and highly chemoselective alkynylation of thiols with hypervalent iodine reagents enabled through a low energy barrier concerted mechanism.
Fast and highly chemoselective alkynylation of thiols with hypervalent iodine reagents enabled through a low energy barrier concerted mechanism.
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通过低能屏障协同机制实现了具有高价值碘试剂的硫醇的快速，高度化学选择性的藻类化。
DOI：
10.1021/ja5083014
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发表时间：
2014-11-26
影响因子：
15
通讯作者：
Waser, Jerome
中科院分区：
文献类型：
--
作者：
Frei, Reto;Wodrich, Matthew D.;Hari, Durga Prasad;Bonin, Pierre-Antoine;Chauvier, Clement;Waser, Jerome
在所有的官能团中，炔烃在合成和药物化学、化学生物学和材料科学中占有特殊的地位。硫代炔尤其有用，因为它们将三键的增强反应性与生物活性化合物和材料中经常遇到的硫原子结合在一起。然而，目前还缺乏获取这些化合物的一般方法。在这篇文章中，我们描述了乙炔基苯并碘化酮(EBX)高价碘试剂用于硫醇的烷基化反应的机理和范围。计算发现了一种新的三原子协同过渡态，它具有非常低的能垒，这使高反应速率合理化。在此基础上，该反应的范围被扩展到合成含有广泛官能团的芳基和烷基取代的炔烃。新的硫代亲核试剂如硫代糖苷、硫代酸和硫化氢钠也被成功地烷基化，从而得到了迄今报道的最通用和最实用的硫代炔的合成方法。
Among all functional groups, alkynes occupy a privileged position in synthetic and medicinal chemistry, chemical biology, and materials science. Thioalkynes, in particular, are highly useful, as they combine the enhanced reactivity of the triple bond with a sulfur atom frequently encountered in bioactive compounds and materials. Nevertheless, general methods to access these compounds are lacking. In this article, we describe the mechanism and full scope of the alkynylation of thiols using ethynyl benziodoxolone (EBX) hypervalent iodine reagents. Computations led to the discovery of a new, three-atom concerted transition state with a very low energy barrier, which rationalizes the high reaction rate. On the basis of this result, the scope of the reaction was extended to the synthesis of aryl- and alkyl-substituted alkynes containing a broad range of functional groups. New sulfur nucleophiles such as thioglycosides, thioacids, and sodium hydrogen sulfide were also alkynylated successfully to lead to the most general and practical method yet reported for the synthesis of thioalkynes.
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影响因子：
4.3
作者：
Brachet, Etienne;Brion, Jean-Daniel;Messaoudi, Samir
通讯作者：
Messaoudi, Samir
影响因子：
1.8
作者：
Bieber, LW;da Silva, MF;Menezes, PH
通讯作者：
Menezes, PH
影响因子：
16.6
作者：
Brand, Jonathan P.;Charpentier, Julie;Waser, Jerome
通讯作者：
Waser, Jerome
影响因子：
2.8
作者：
Chandanshive, Jay Zumbar;Bonini, Bianca Flavia;Franchini, Mauro Comes
通讯作者：
Franchini, Mauro Comes
影响因子：
5.2
作者：
Dunetz, JR;Danheiser, RL
通讯作者：
Danheiser, RL