Mechanistic insights on reduction of carboxamides by diisobutylaluminum hydride and sodium hydride−iodide composite

Mechanistic insights on reduction of carboxamides by diisobutylaluminum hydride and sodium hydride−iodide composite

The reaction mechanisms on reduction of tertiary carboxamides by diisobutylaluminum hydride (DIBAL) and sodium hydride (NaH)-sodium iodide (NaI) composite were elucidated by the computational and experimental approaches. Reduction of N,N-dimethyl carboxamides with DIBAL provides the corresponding am...

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Bibliographic Details
Main Authors: Ong, Derek Yiren, Watanabe, Kohei, Takita, Ryo, Chiba, Shunsuke
Other Authors: School of Physical and Mathematical Sciences
Format: Article
Language:English
Published: 2022
Subjects:
Science::Chemistry
Amides
Reduction
Online Access:https://hdl.handle.net/10356/154840
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Institution: Nanyang Technological University
Language: English
Description
Summary:The reaction mechanisms on reduction of tertiary carboxamides by diisobutylaluminum hydride (DIBAL) and sodium hydride (NaH)-sodium iodide (NaI) composite were elucidated by the computational and experimental approaches. Reduction of N,N-dimethyl carboxamides with DIBAL provides the corresponding amines, whereas that with the NaH−NaI composite exclusively forms aldehyde even at high reaction temperature. DFT calculations revealed that dimeric structural nature of DIBAL and Lewis acidity on its Al center play crucial role to decompose the tetrahedral anionic carbinol amine intermediate through C−O bond cleavage. On the other hand, in the reduction with the NaH−NaI composite, the resulting tetrahedral anionic carbinol amine intermediate could be kept stable, thus providing aldehydes as a sole product by the aqueous workup.

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