Domino allylic alkylation

The key step is the synthesis of the metathesis precursor, which was required in both the cis- and trans- configurations. The cz .v-configuration was obtained via enantioselective domino allylic alkylations (Scheme 6, 15a and 15b). For the rra/zs-configuation, an allylic alkylation was used to introduce the first amine, but the second amine was introduced via the Mitsunobu reaction25 to achieve an inversion of the stereocentre (Scheme 6,16a and 16b). 

More recently this group has prepared a combination of palladium and cobalt nanoparticles immobilized on silica (PCNS) to form bicyclic enones after domino allylic alkylation-PKR [130]. 

Scheme 11.14 Domino regio-and diastereoselective r-allyl alkylation and PK reaction.

Chen and coworkers published a formal [3 + 3]-type reaction to give highly substituted cyclohexenes 8. This domino process consists of an allylic-allylic alkylation of an a,a-dicyanoalkene derived from 1-indanone and Morita-Baylis-Hillman carbonates, following an intramolecular Michael addition, by employing dual orga-nocatalysis of commercially available modified cinchona alkaloid (DHQD)2AQN If (hydroquinidine (anthraquinone-l,4-diyl) diether) and (S)-BINOL. The cyclic adducts... 

Ashfeld et al. expanded the scope of this Rh-catalyzed domino reaction to other types of cycloadditions. It was reported that [Rh(CO)2Cl]2 was an effective catalyst for allylic alkylation with high regioselectivity. When an enantiomerically pure carbonate was employed, the allylic alkylation gave the product with retention of absolute configuration (98% ee). In addition to studying allylic alkylation reactions, a series of novel domino reactions such as cycloisomerizations and [5+2] cycloadditions was explored (Scheme 2-93). ... 

Scheme 12.95 Rh-catalyzed allylic alkylation domino reactions [199],...

Scheme 3.3 Domino conjugate reduction-allylic alkylation reaction catalysed by a combination of copper catalysis and chiral palladium catalysis.

Palladium-catalyzed carbopalladation/allylic alkylation domino sequence. 

A combination of a Tsuji-Trost and a Michael addition was used for the synthesis of (+)-dihydroerythramine 6/1-269, as reported by Desmaele and coworkers [128]. The Pd-catalyzed reaction of the allylic acetate 6/1-267 with the nitromethylarene 6/1-266 in the presence of Cs2C03 as base led to the domino product 6/1-268 as a 4 1 mixture of two diastereomers in 79% yield. Further manipulation of 6/l-268a yielded the desired dihydroerythramine 6/1-269 (Scheme 6/1.70). Interestingly, using the corresponding allylic carbonate without additional base gave the mono-alkylated product only. 

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