Pd0 -Catalyzed Asymmetric Carbonitratation Reaction Featuring an H-Bonding-Driven Alkyl-PdII -ONO2 Reductive Elimination.
Angew Chem Int Ed Engl
; 62(3): e202215397, 2023 01 16.
Article
in En
| MEDLINE
| ID: mdl-36420824
ABSTRACT
Reductive elimination of alkyl-PdII -O is a synthetically useful yet underdeveloped elementary reaction. Here we report that the combination of an H-bonding donor [PyH][BF4 ] and AgNO3 additive under toluene/H2 O biphasic system can enable such elementary step to form alkyl nitrate. This results in the Pd0 -catalyzed asymmetric carbonitratations of (Z)-1-iodo-1,6-dienes with (R)-BINAP as the chiral ligand, affording alkyl nitrates up to 96 % ee. Mechanistic studies disclose that the reaction consists of oxidative addition of Pd0 catalyst to vinyl iodide, anion ligand exchange between I- and NO3 - , alkene insertion and SN 2-type alkyl-PdII -ONO2 reductive elimination. Evidences suggest that H-bonding interaction of PyHâ
â
â
ONO2 can facilitate dissociation of O2 NO- ligand from the alkyl-PdII -ONO2 species, thus enabling the challenging alkyl-PdII -ONO2 reductive elimination to be feasible.
Key words
Full text:
1
Collection:
01-internacional
Database:
MEDLINE
Main subject:
Palladium
/
Alkenes
Language:
En
Journal:
Angew Chem Int Ed Engl
Year:
2023
Document type:
Article
Affiliation country:
China