Copper-catalyzed carbonylative catenation of olefins: Direct synthesis of γ-boryl esters

Iron-catalyzed regioselective protoboration of alkenes on N-heterocycles

“…17 Meanwhile, the reaction of DMA with LiO t Bu produced tertiary butanol. 6 g ,18 Upon further protonation using butanol as a proton source, the desired product 2 or 4 was afforded. 7 b ,8 Then the key intermediate I was regenerated by the reaction of III with B 2 pin 2 to complete the catalytic cycle.…”

Non‐Noble Metal‐Catalyzed Carbonylative Multi‐Component Reactions

“…γ ‐Boryl esters were prepared from the β ‐substituted styrenes and alcohols in moderate to good yields, via carbonylative borofunctionalization in the presence of CuI and dppe catalytic system (Scheme 16). 13 C‐labeling experiment showed the −CH 2 −CO− fraction was derived from the carbon monoxide that acyl‐copper intermediate A, generated from the CO insertion of β ‐boryl alkyl copper species I , in‐situ isomerized to carbene intermediate B , which coordinate with another molecular of CO to ketene intermediate, following react with sodium alcoholate and B 2 pin 2 to γ ‐boryl esters [18] …”

“…13 C-labeling experiment showed the À CH 2 À COÀ fraction was derived from the carbon monoxide that acyl-copper intermediate A, generated from the CO insertion of β-boryl alkyl copper species I, in-situ isomerized to carbene intermediate B, which coordinate with another molecular of CO to ketene intermediate, following react with sodium alcoholate and B 2 pin 2 to γ-boryl esters. [18] With the assistance of copper catalysts, some CF 3 sources can generate CF 3 radical or CuCF 3 species, then added to CÀ C unsaturated bonds to a new radical or cationic species, which can be trapped by nucleophiles. In the CO atmosphere, a similar reaction process involving carbonylation was reported by Wu and co-workers (Scheme 17).…”

Copper-Catalyzed Synthesis of Multideuterium-Labeled Alcohols from Styrenes with CO and D2 as the Source of the Hydroxymethyl Group

“…Recently, our group developed several copper-catalyzed organic transformations with CO as the carbon or carbonyl source. , In our latest work on Cu-catalyzed carbonylation reactions, we found that carbon carbene species can be formed as key intermediates and were ready for further transformations . Hence, we believe that the carbene species III , which isomerizes from the acyl copper complex via a three-membered-ring state, can also be captured by D 2 .…”

“…Based on these experimental results and literature precedent, ,, the proposed mechanism of this reaction of styrenes is shown in Figure . Initially, the (L)­Cu–D complex was produced in the presence of NaO t Bu and D 2 .…”