Decarboxylative Alkynylation.

Decarboxylative Alkynylation.
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DOI:
10.1002/anie.201705107
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发表时间:
2017-09-18
期刊:
Angewandte Chemie (International ed. in English)
影响因子:
--
通讯作者:
Baran PS
Baran PS
中科院分区:
其他
文献类型:
--
作者:
Smith JM;Qin T;Merchant RR;Edwards JT;Malins LR;Liu Z;Che G;Shen Z;Shaw SA;Eastgate MD;Baran PS

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The development of a new decarboxylative cross-coupling protocol that affords terminal and substituted alkynes from various carboxylic acids is described using both nickel- and iron-based catalysts. The use of N-hydroxytetrachlorophthalimide (TCNHPI) esters is crucial to the success of the transformation, and the reaction is amenable to in situ carboxylic acid activation. Additionally, an inexpensive, commercially-available alkyne source is employed in this formal homologation process that serves as a surrogate for other well-established alkyne syntheses. The reaction can be conducted on a mole scale, and the conditions are mild, operationally simple, and broad in scope while providing succinct avenues to previously reported synthetic intermediates. All kinds of Alkynes: A convenient method for the decarboxylative alkynylation of redox active esters has been developed. The reaction is broad, functional group tolerant, and provides access to alkynes that are both terminal and substituted using either Ni or Fe catalysis. The method is used to swiftly synthesize a variety of alkynyl intermediates that were previously difficult to access using conventional alkynylation strategies.
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