1222-01-1Relevant academic research and scientific papers
Steric Influence on Reactions of Benzyl Potassium Species with CO
Wang, Tongtong,Xu, Maotong,Jupp, Andrew R.,Qu, Zheng-Wang,Grimme, Stefan,Stephan, Douglas W.
supporting information, p. 3640 - 3644 (2021/10/19)
Reactions of benzyl potassium species with CO are shown to proceed via transient carbene-like intermediates that can undergo either dimerization or further CO propagation. In a sterically unhindered case, formal dimerization of the carbene is the dominant reaction pathway, as evidenced by the isolation of ((Ph3SiO)(PhCH2)C)2 2 and PhCH2C(O)CH(OH)CH2Ph 3. Reactions with increasingly sterically encumbered reagents show competitive reaction pathways involving intermolecular dimerization leading to species analogous to 2 and 3 and those containing newly-formed five-membered rings tBu2C6H2(C(OSiR3)C(OSiR3)CH2) (R=Me 6, Ph 7). Even further encumbered reagents proceed to either dimerize or react with additional CO to give a ketene-like intermediates, thus affording a 7-membered tropolone derivative 14 or the dione (3,5-tBu2C6H3)3C6H2CH2C(O))2 15.
Photoreaction of a Stable Thioaldehyde 2,4,6-Tri-tert-butylthiobenzaldehyde
Cremonini, Mauro A.,Lunazzi, Lodovico,Placucci, Giuseppe,Kumon, Naoko,Ishii, Akihiko,et al.
, p. 1045 - 1049 (2007/10/02)
The photochemical reaction of the only isolable aromatic thioaldehyde ArCHS (1; Ar=2,4,6-tri-tert-butylphenyl) in alkaline medium yields ArCH2CH2Ar (2), ArCH2SCH2Ar (3), 6,8-di-tert-butyl-3,4-dihydro-4,4-dimethyl-1H-2-benzothiine (4) and ArMe (5).A radica
