Fig. 3: Mechanistic experiments. | Nature Chemistry

Fig. 3: Mechanistic experiments.

From: Chelation enables selectivity control in enantioconvergent Suzuki–Miyaura cross-couplings on acyclic allylic systems

Fig. 3: Mechanistic experiments.The alternative text for this image may have been generated using AI.

a, Reactions using enantiopure (99% e.e.) (S)-1 starting material and different enantiomers of ligand (L). The S ligand gives an excellent Z/E ratio and 98% e.e., while the R ligand gives an ~1:1 mixture of double bond isomers and <95% e.e. b, Following a reaction with (±)-1 over time (bottom plot) shows that when using boronic acid 2b, as in the schematic (top), the product Z/E ratio decreases over time, and that one enantiomer of the starting material (SM) preferentially reacts so that the starting material becomes enantiomerically enriched. c, Control experiments with alternative allylic carbonates are consistent with the idea that γ-arylation can be achieved on allylic enones where the rhodium can chelate to the carbonyl, as 14, 16, 17 and 18 did not undergo allylic arylation. d, Control experiments using allylic carbonates with different carbonyl groups suggest that the directing or chelating ability of the carbonyl plays a key role in the selectivity of these reactions. R2, coefficient of determination.

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