Abstract
Chiral non-racemic allylic species are key building blocks in the synthesis of a wide range of important
carbon-containing molecules, including pharmaceuticals and polymers. Metal-catalyzed asymmetric
additions of nucleophiles to allylic species undergo different reaction pathways depending on the
combination of metal and nucleophile used, which has hindered the development of broadly useful
addition reactions with aromatic nucleophiles. Here, we report an asymmetric cross-coupling method
between aryl boronic acids and linear allylic phosphates to give branched allylic products. This Suzukitype reaction overcomes the ‘memory effect’ in Rh-catalysis to allow an overall SN2’ transformation by
rate-determining reductive elimination and forms a new stereogenic centre adjacent to a terminal vinyl
moiety. The method tolerates pre-existing stereogenic centres allowing the development of synthetic
strategies where drugs and natural products are elaborated via diastereoselective allylic arylations. The
method is used, as the catalyst-controlled stereochemistry-setting step, in an iterative synthetic strategy
to give arrays of aryl substituted contiguous stereogenic centres, and we anticipate this approach will be
a useful compliment to existing catalyst controlled stereoselective methods for forming C-C bonds.
Supplementary materials
Title
Supplementary materials
Description
Experimental procedures, characterization of compounds, SFC/HPLC spectra, crystal structure.
Actions
Title
Checkcif for (R,R)-63
Description
Checkcif for (R,R)-63
Actions
Title
CIF file for (R,R)-63
Description
CIF file for (R,R)-63
Actions