Figure 4: Scope of electrophiles in the catalyst-controlled regiodivergent Suzuki Miyaura cross-coupling with dehydropiperidyl boronate 4.

In the chemical equation on the top, variation of the R group in the electrophile under conditions of the left hand reaction provides via α coupling the 4-substituted dehydropiperidine products shown. Application of the γ coupling conditions on the right hand reaction provides the 2-substituted products. Below the structures of products, the isolated yield of the major, separated regioisomer is indicated in brackets next to the product number. Regioisomer ratio (α/γ) was measured from the ¹H NMR spectra of crude products, and, unless indicated otherwise,^a the er was obtained directly from the pure coupling products by chiral HPLC analysis with a reasonable error of 2%. Note. Reaction conditions and scale are indicated in Table 2 and Methods. See Table 1 for structure of Xphos and Pd-PEPPSI-i-Pr. ^aer was measured after chemical derivatization as outlined in the Supplementary Information. ^bProduct prepared from the enantiomeric substrate (R)-4. ^cTetrahydrofuran, 70 °C. ^dProduct prepared from a 4:1 E/Z mixture of β-bromostyrene. The E isomer reacts selectively and the Z isomer is recovered unreacted. t-Boc, tert-butoxycarbonyl: (CH₃)₃COCO.