ChemInform Abstract: SILICON‐CONTAINING IMINES OF ETHYNE ALDEHYDES; SYNTHESIS AND REACTIONS WITH COMPLEX METAL HYDRIDES

Suvorova, I. V.; Stadnichuk, M. D.

doi:10.1002/chin.198229184

Cited by 1 publication

(1 citation statement)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Normant et al described in 1973 a synthetic pathway for the preparation of 1-aza-but-1-en-3-ynes, based on the formation of intermediate lithium cuprates, which were reacted with N -phenyl-benzimidoyl chloride . Stadnichuk et al and Vyazankin et al published in 1982 and 1983, respectively, a simple synthetic pathway to 1-aza-but-1-en-3-ynes by condensing trimethylsilyl-substituted propargylaldehydes with aliphatic and aromatic amines. Recently, Micouin et al published a new access to α-silylated alkynylhydrazones by treatment of dimethylaluminum alkynides with trimethylsilyldiazomethane …”

Section: Introductionmentioning

confidence: 99%

Chemoselective Hydroalumination of 1-Aza-but-1-en-3-ynes (C-Iminoalkynes): Formation of Propargylamines by Imine Reduction and of 5-Aluminazoles and 1-Aza-butadienes by Anti-Michael Attack

et al. 2018

View full text Add to dashboard Cite

Hydroalumination of 1-aza-but-1-en-ynes 1 provides facile access to propargylamines 4 by reduction of the CN bonds or alternatively to 1-aza-buta-1,3-dienes 6 by reduction of the triple bond. The chemoselectivity depends not only on the steric properties of both the hydroalumination agent (di-iso-butylaluminum (DIBAL-H, iBu 2 AlH) versus ditert-butylaluminum hydride (tBu 2 AlH)) and the substrates but also on the reaction temperatures. In several cases, initial aluminum species of 5-aluminazole type 5 could be isolated and characterized by X-ray diffraction, indicating an "anti-Michael" addition of the hydride to the triple bond. Aqueous workup of those species led to 1-azabutadiene derivatives 6. High-level DFT calculations indicate that the observed chemoselectivity is only compatible with a dimeric nature of the hydroaluminating agent. Using such a dimer, the imine reduction corresponds to the kinetically controlled pathway, whereas the triple bond reduction leads to the thermodynamically much more stable 5-aluminazoles, 5.

show abstract

Section: Introductionmentioning

confidence: 99%

Chemoselective Hydroalumination of 1-Aza-but-1-en-3-ynes (C-Iminoalkynes): Formation of Propargylamines by Imine Reduction and of 5-Aluminazoles and 1-Aza-butadienes by Anti-Michael Attack

et al. 2018

View full text Add to dashboard Cite

show abstract

ChemInform Abstract: SILICON‐CONTAINING IMINES OF ETHYNE ALDEHYDES; SYNTHESIS AND REACTIONS WITH COMPLEX METAL HYDRIDES

Abstract: Aus dem Trimethylsilyl‐propinal (I) und den Aminen (II) erhält man die En‐ine (III).

Cited by 1 publication

References 0 publications

Chemoselective Hydroalumination of 1-Aza-but-1-en-3-ynes (C-Iminoalkynes): Formation of Propargylamines by Imine Reduction and of 5-Aluminazoles and 1-Aza-butadienes by Anti-Michael Attack

Chemoselective Hydroalumination of 1-Aza-but-1-en-3-ynes (C-Iminoalkynes): Formation of Propargylamines by Imine Reduction and of 5-Aluminazoles and 1-Aza-butadienes by Anti-Michael Attack

Contact Info

Product

Resources

About