Conformational Preferences of a Tropos Biphenyl Phosphinooxazoline-a Ligand with Wide Substrate Scope

• Excellent enantioselectivities are observed in palladium-catalyzed allylic substitutions of a wide range of substrate types and nucleophiles using a bidentate ligand composed of oxazoline and chirally flexible biaryl phosphite elements. This unusually wide substrate scope is shown by experimental and theoretical studies of its eta(3)-allyl and eta(2)-olefin complexes not to be a result of configurational interconversion of the biaryl unit, since the ligand in all reactions adopts an S-a,S configuration on coordination to palladium, but rather the ability of the ligand to adapt the size of the substrate-binding pocket to the reacting substrate. This ability also serves as an explanation to its excellent performance in other types of catalytic processes.

Ämnesord

NATURVETENSKAP  -- Kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences (hsv//eng)

NATURVETENSKAP  -- Kemi -- Organisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Organic Chemistry (hsv//eng)

Nyckelord

palladium

allylic substitution

tropos P

N-ligands

NMR study

DFT study

catalyzed allylic substitution

molecular-orbital methods

phosphite-oxazoline ligands

asymmetric catalysis

conjugate addition

enantioselective synthesis

diphosphite ligands

aliphatic-alcohols

metal-complexes

chiral ligands

Chemistry

ertus s

1982

chemical physics

v65

p239

lean ad

1980

journal of chemical physics

v72

p5639

palladium

Publikations- och innehållstyp

ref (ämneskategori)

art (ämneskategori)