2011
DOI: 10.3390/molecules16010951
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Palladium Catalyzed Allylic C-H Alkylation: A Mechanistic Perspective

Abstract: The atom-efficiency of one of the most widely used catalytic reactions for forging C-C bonds, the Tsuji-Trost reaction, is limited by the need of preoxidized reagents. This limitation can be overcome by utilization of the recently discovered palladium-catalyzed C-H activation, the allylic C-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic a… Show more

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Cited by 75 publications
(13 citation statements)
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References 87 publications
(119 reference statements)
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“…The deuterium kinetic isotope effect observed during the burst supports allylic C-H activation as the rate-limiting step during this phase. 90,94,95 The resulting allyl-Pd II intermediate undergoes reductive elimination of cinnamyl acetate to afford a Pd 0 species that reacts with a DAF/Pd II (OAc) 2 species to afford the Pd I dimer 2 (Scheme 3; cf. Figure 14).…”
Section: Analysis Of the Burst Phase Of The Reactionmentioning
confidence: 99%
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“…The deuterium kinetic isotope effect observed during the burst supports allylic C-H activation as the rate-limiting step during this phase. 90,94,95 The resulting allyl-Pd II intermediate undergoes reductive elimination of cinnamyl acetate to afford a Pd 0 species that reacts with a DAF/Pd II (OAc) 2 species to afford the Pd I dimer 2 (Scheme 3; cf. Figure 14).…”
Section: Analysis Of the Burst Phase Of The Reactionmentioning
confidence: 99%
“…41,[105][106][107] As noted in the Introduction, very few mechanistic studies of Pd-catalyzed allylic oxidation reactions have been reported. The two most thorough precedents were reported recently by the groups of Labinger/Bercaw 10 and Fristrup, 94 and focused on bipyrimidine (bpym)/ Pd II (OAc) 2 and bis(sulfoxide)/Pd II (OAc) 2 catalyst systems, respectively. The turnoverlimiting step in the former reaction was identified as alkene binding to (bpym)Pd II (OAc) 2 , while the latter reaction was attributed to C-H activation.…”
Section: Analysis Of the Post-burst Phase Of The Reactionmentioning
confidence: 99%
“…When an alkene coordinates to a PdX 2 complex, the electronic character of the olefin π-system changes enabling two main and mutually excluding reaction paths, namely nucleopalladation [1][2][3][4][5][6] or C-H allylic activation [7][8][9][10][11][12] to provide an electrophilic η 3 -allylpalladium complex. Other reactions and intermediates are also accessible depending upon the nature of the starting alkene and/or the reaction conditions (Scheme 1) [13].…”
Section: Introductionmentioning
confidence: 99%
“…In the case of the ladder polyether metabolites, the biosynthetic order is reversed in that a linear precursor is oxidized, then cyclized. Composed of a series of fused small (five-membered) to medium (nine-membered) cyclic ethers, this family is arguably the most complex set of natural products ever to be isolated, and it includes such daunting structures as brevetoxin B (23) 30 , yessotoxin (24) 31 and maitotoxin (25; Fig. 3a) 32 .…”
Section: Overturning Chemical 'Rules'mentioning
confidence: 99%