Carbon–Oxygen Bond Activation in Esters by Platinum(0): Cleavage of the Less Reactive Bond

Abstract

Reaction of Pt(dippe)(NBE)2 (NBE = norbornene) with a variety of esters leads to a product in which the less reactive C–O bond is cleaved to give Pt(dippe)(O2CR)(R′). A further disproportionation reaction occurs to eliminate R′2 and produce Pt(dippe)(O2CR)2. Details of the mechanisms of these reactions are explored.

Few layer 2D pnictogens catalyze the alkylation of soft nucleophiles with esters

“…Nature makes use of alkyl phosphates, sulphonates, and esters as alkylating agents, under metal-free physiological conditions 10,11 . In contrast, synthetic methods generally employ energetically higher alkyl halides and alcohols as alkylating agents under very strong basic or acidic conditions (i.e., Williamson synthesis) 12 , and the synthetic alkylation protocols reported with poly-oxygenated compounds need expensive and toxic metal catalysts, such as the palladium-catalyzed Tsuji–Trost allylation reaction 13 , the Hantzsch ester-assisted hafnium-catalyzed alkylation of quinones 14 , and the gold-catalyzed alkylation with alkynylbenzoic acids 15 , among some others 16,17 . Thus, the discovery of a simple, metal-free, biomimetic alkylation reaction with readily available poly-oxygenated molecules 18 remains a challenge in organic synthesis and catalysis, furthermore attractive if selective and functional-group tolerant 19,20 .…”

Oxidative addition of ether O-methyl bonds at a Pt(0) centre

“…[5][6][7][8] The related oxidative addition of ether C-O bonds appears to be missing from the literature although examples of C-O reductive elimination of ethers from Pd(II) are known. 9,10 In contrast, C-O (ester) oxidative addition at Pt(0) has recently been described 11 and reductive elimination of ester C-O bonds from Pd(IV) and Pt(IV) is well known. [12][13][14] We demonstrate the importance of electron withdrawing aryl groups for achieving oxidative addition of methyl aryl ethers at Pt(0) and probe the mechanism of C-O activation.…”

Activation of C–O and C–F Bonds by Pincer–Iridium Complexes

“…During the course of this work, Ozerov et al and Jones et al [48,49] reported C(sp 3 )-O bond addition in the reactions of benzyl methyl ether with an Ir complex and methyl benzoate with a Pt complex, respectively. …”