Paramagnetic 1H-NMR relaxation probes of stereoselectivity in metalloporphyrin catalyzed olefin epoxidation.

Abstract:

:Enantioselective catalytic epoxidation of olefins is an important problem from both practical and mechanistic points of view. The origins of chiral induction by asymmetric porphyrin and salen complexes were investigated by FT-NMR T1 relaxation techniques. A new chiral vaulted porphyrin (1) that carries (S)-binaphthyl-L-alanine straps across both faces of the porphyrin macrocycle was synthesized and characterized. (R)-styrene oxide was obtained in > 90% ee in the initial stages of styrene epoxidation with F5PhIO catalyzed by 1-Fe(III)Cl. The transition state for olefin epoxidation with high-valent metal-oxo species was modeled by coordinating epoxides to paramagnetic copper complexes of the corresponding ligands. The epoxide enantiomer that better fit the chiral cavity of the catalyst, as revealed by T1 relaxation measurements, was also the major product of catalytic olefin epoxidation. These results are consistent with the "lock-and-key" mechanism of asymmetric catalysis by metalloporphyrins. The copper complex of a chiral salen ligand showed no differentiation in terms of T1 relaxation rates between the enantiomers of cis-beta-methylstyrene oxide in contrast to the high enantioselectivity observed for catalytic epoxidation.

journal_name

Chirality

journal_title

Chirality

authors

Groves JT,Crowley SJ,Shalyaev KV

subject

Has Abstract

pub_date

1998-01-01 00:00:00

pages

106-19

issue

1-2

eissn

0899-0042

issn

1520-636X

pii

10.1002/(SICI)1520-636X(1998)10:1/2<106::AID-CHIR1

journal_volume

10

pub_type

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