3010-80-8Relevant articles and documents
Shuttle arylation by Rh(I) catalyzed reversible carbon–carbon bond activation of unstrained alcohols
Lutz, Marius D.R.,Gasser, Valentina C.M.,Morandi, Bill
supporting information, p. 1108 - 1119 (2021/04/19)
The advent of transfer hydrogenation and borrowing hydrogen reactions paved the way to manipulate simple alcohols in previously unthinkable manners and circumvented the need for hydrogen gas. Analogously, transfer hydrocarbylation could greatly increase the versatility of tertiary alcohols. However, this reaction remains unexplored because of the challenges associated with the catalytic cleavage of unactivated C–C bonds. Herein, we report a rhodium(I)-catalyzed shuttle arylation cleaving the C(sp2)–C(sp3) bond in unstrained triaryl alcohols via a redox-neutral β-carbon elimination mechanism. A selective transfer hydrocarbylation of substituted (hetero)aryl groups from tertiary alcohols to ketones was realized, employing benign alcohols as latent C-nucleophiles. All preliminary mechanistic experiments support a reversible β-carbon elimination/migratory insertion mechanism. In a broader context, this novel reactivity offers a new platform for the manipulation of tertiary alcohols in catalysis.
Facile preparation of aromatic esters from aromatic bromides with ethyl formate or DMF and molecular iodine via aryllithium
Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
scheme or table, p. 4701 - 4709 (2012/07/28)
Various aromatic bromides were treated with n-BuLi and subsequently with ethyl formate, followed by the reaction with ethanol and molecular iodine in the presence of K2CO3 to provide the corresponding aromatic ethyl esters in good yields. Moreover, aromatic bromides could be transformed into the corresponding aromatic methyl esters in good yields by the treatment with n-BuLi and subsequently with DMF, followed by the reaction with methanol, molecular iodine, and K2CO3. Some aromatics could be also converted into the corresponding aromatic esters in good yields by the treatment with n-BuLi, and subsequently with ethyl formate or DMF, followed by the reaction with molecular iodine and K2CO3. The present reactions offer a novel route for the transition-metal-free, carbon-monoxide-free, and therefore environmentally benign one-pot conversion of aromatic bromides and aromatics into aromatic esters.
Thioether complexes of tungsten hexacarbonyl
Lucas, C. Robert
, p. 1758 - 1763 (2007/10/02)
The preparation of a series of organic and organometallic thioethers R3MSR' (M = C,Si,Ge, or Sn) is reported.From these, several new compounds of type 1 are synthesized, some of which contain para-substituted aryl functions for R and R'.In hexane solution in the carbonyl streching region of the ir the uv there is evidence for a degree of multiple bonding, at least in the M - S - WW - CO portion of these molecules.Multiple bonding extending into aromatic R or R'is small or non-existent and cannot be assessed precisely because of spontaneous decomposition of the complexes.All the complexes undergo a thermally initiated decomposition, the case of which depends on the nature of R, R', and M.The unusual W(I) thiolate cis-2 is the termal decomposition product.
