[IrCp*(NCMe)₂(PPh₂Me)][PF₆]₂ as Catalyst for the Meyer–Schuster Rearrangement of Arylpropargylic Alcohols under Mild Conditions

Abstract

The novel iridium complex [IrCp*(NCMe)2(PPh2Me)][PF6]2 (I) efficiently catalyzed the Meyer–Schuster rearrangement of selected arylpropargylic alcohols into α,β‐unsaturated aldehydes under mild conditions and without the need of a co‐catalyst. A mechanism involving a (hydroxy)alkenylcarbene intermediate is proposed.

Recent Developments in the Meyer‐Schuster Rearrangement

“…[35] The iridium complex 32, at 5 mol% in dichloromethane at room temperature, gave a small library of conjugated enals. [36] On the other hand, the readily available complex [V(O)Cl(OEt) 2 ] 34 b, in toluene at 80°C and under microwave irradiation, also gave MSR products in good yields. [37] The MSR could be employed also for a novel preparation of useful α,β-unsaturated acylsilanes 38, as indicated in Scheme 4.…”

Palladium‐Catalyzed Cascade Saegusa–Heck Reaction: Synthesis of β,β‐Diarylacroleins from Arylpropanals and Aryl Iodides

“…The trans/cis configurations of 8d , 8h , 8j , 8k , and 8p (Table ) were identified by comparison with the spectroscopic data reported in the literature ,. [7b], [8b], The results indicate that the major products adopted the trans geometry. Additionally, upon using 7b as a substrate (Table , entries 2 and 20), more isomers were detected by NMR spectroscopy owing to the steric effect of the ortho ‐methyl group (see the Supporting Information).…”

Confined surface-enhanced indole cation-radical cyclization studied by mass spectrometry

“…Significantly, after 6 min of the reaction, the product ion at m/z 184 came to be the main peak, while other ions, including reactant ion (m/z 119) and [3- It should be noted that the generation of 4 without deuteration could be attributed to the rapid hydrogen-deuterium exchange or the mediation of counteranion PF 6 − . 27 The online extracted ion chromatograms (EICs) of deuterated ions also indicated the consumption of the reactant 1-d 1 (Fig. S5-a †), along with the generation of product 4 (Fig.…”