Palladium‐Catalyzed/Lewis Acid‐Promoted Alkene Dimerization and Cross‐Coupling with Alcohols via CH Bond Activation

Abstract

Abstract:The cross-couplings of alcohols to alkenes with the palladium/Lewis acid system are reported. This reaction occurs in a successive alkene dimerization, direct C À H activation of alcohol and sp 3 À sp 3 bond forming sequence via an interesting domino process.

Direct Sp3α-C–H activation and functionalization of alcohol and ether

“…Our group has developed several protocols for this reaction type. [68][69][70][71][72][73][74] In 2005, we occasionally found in a synthetic experimental that a secondary alcohol was formed as a by-product through the direct coupling of primary alcohol at the a-position with styrene under the co-promotion of RhCl(PPh 3 ) 3 and BF 3 Á OEt 2 . 68 This observation let us establish, for the first time, the direct coupling protocol of unprotected alcohols 87 with alkenes 88 to the secondary alcohols 89 via C-H activation (Scheme 29, eqn (1)).…”

“…In 2008, 69 our further investigation resulted in the development of a tandem C-C bond coupling protocol of alcohol 87 with two alkene molecules 88 and 90 under co-promotion of Pd(OAc) 2 (cat. )/BF 3 ÁOEt 2 (excess) in MeNO 2 at 60 1C, which involves firstly a dimerization of two alkene molecules 88 and 90, and then coupling with alcohol 87 via sp 3 C-H activation to give rise to the secondary alcohol 91 (Scheme 29, eqn ( 2)).…”

Molecular iodine as a mild catalyst for cross-coupling of alkenes and alcohols

“…The majority of known methods include the use of very effective transition metal catalysts, such as complexes of Pd, Cu, Ni, Fe, Ru and Lewis acids based on weak metals (e.g. Bi, In and Ga) [7][8][9][10][11][12][13][14][15][16][17]. However, toxicity of organometallic reagents and their removal to meet the strict specifications of pharmaceutical grade purity is a challenging and demanding process.…”

Theoretical investigation on the mechanism of FeCl3-catalysed cross-coupling reaction of alcohols with alkenes

“…Many detailed theoretical investigations have been done to understand the reaction mechanisms of the significant palladium-catalysed [19][20][21][22][23][24][25][26] and nickel-catalysed [27][28][29][30][31] reactions, ever since the modern transition-metal-catalysed cross-coupling reactions emerged in the 1970s [32][33][34][35]. However, detailed * Corresponding author.…”