278 15 APRIL 2022¥VOL 376 ISSUE 6590 science.orgSCIENCE
Fig. 2. AACC reaction scope.(A) Aliphatic cyclic and acyclic amine scope,
including the top five aliphatic tertiary amines found in medicinal chemistry.
(B) Terminal olefin scope. All reactions were run under ambient conditions.
Unless otherwise indicated, all reactions were run on a 0.2-mmol scale using
amine-BF 3 (1 equivalent), olefin (1 equivalent), Pd(OAc) 2 (10 mol %), (±)-MeO-SOX
(10 mol %), 2,5-dimethyl-1,4-benzoquinone (2,5-DMBQ) (1.1 equivalents), and
dbp in solvent (1 M) at 45°C for 48 hours, followed by basic workup. All amination
products were formed in >20:1 L:B and >20:1E:Zselectivity, and isolated yields
of the free tertiary amine products are the average of three experiments.
*25% dbp in dioxane.†50% dbp in dioxane.‡25% dbp in toluene (in some
cases, toluene diminishes diene by-product formation). §50% dbp in toluene.
¶5% dbp in dioxane. #0.5 equivalents of amine-BF 3. **0.4-mmol scale.
††5 mol % (±)-MeO-SOX·Pd(OAc) 2 .‡‡0.167 M. §§0.4 M. ¶¶12 hours. ##24 hours.
***72 hours.†††Average of two experiments.RESEARCH | REPORTS