7239-24-9Relevant articles and documents
Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application
Han, Bo,Jiao, Haijun,Wu, Lipeng,Zhang, Jiong
, p. 2059 - 2067 (2021/09/02)
Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C–O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C–N bond cleavage-reformation process, followed by C–O bond cleavage.
Supramolecular Ga4L612- cage photosensitizes 1,3-rearrangement of encapsulated guest via photoinduced electron transfer
Dalton, Derek M.,Ellis, Scott R.,Nichols, Eva M.,Mathies, Richard A.,Dean Toste,Bergman, Robert G.,Raymond, Kenneth N.
supporting information, p. 10128 - 10131 (2015/09/01)
The K12Ga4L6 supramolecular cage is photoactive and enables an unprecedented photoreaction not observed in bulk solution. Ga4L612- cages photosensitize the 1,3-rearrangement of encapsulated cinnamylammonium cation guests from the linear isomer to the higher energy branched isomer when irradiated with UVA light. The rearrangement requires light and guest encapsulation to occur. The Ga4L612- cage-mediated reaction mechanism was investigated by UV/vis absorption, fluorescence, ultrafast transient absorption, and electrochemical experiments. The results support a photoinduced electron transfer mechanism for the 1,3-rearrangement, in which the Ga4L612- cage absorbs photons and transfers an electron to the encapsulated cinnamylammonium ion, which undergoes C-N bond cleavage, followed by back electron transfer to the cage and recombination of the guest fragments to form the higher energy isomer.
Spiroborate catalyzed reductions with N,N-diethylaniline borane
Coleridge, Brian M.,Angert, Thomas P.,Marks, Lucas R.,Hamilton, Patrick N.,Sutton, Christopher P.,Matos, Karl,Burkhardt, Elizabeth R.
supporting information; experimental part, p. 5973 - 5976 (2010/11/21)
Reduction of esters, amides, and ketones by N,N-diethylaniline borane is accelerated by catalysts derived from spiroborate complexes. Esters are reduced at ambient temperature in less than 4 h with this amine borane and 5 mol % spiroborate 6. Functional group selectivity shows ketone and tertiary amide reduction is faster than ester or nitrile reduction.
