Development of Enantioselective Nitrogen Arylation Reactions

ACS PRF #49493-UR1 PPh2 OMe N H O N H O R R pro-R pro-S Br N H O N H O R R pro-R pro-S Pd (R)-MOPn Br N Pd N H O R O R (R)-MOPn ...
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Development of Enantioselective Nitrogen Arylation Reactions Russell D. Viirre Dept. of Chemistry and Biology, Ryerson University, Toronto, Ontario, Canada

pro-R R N H

O

O

pro-S R N H

Br

pro-R O R N H

"(R)-MOP palladium(0) complex" oxidative addition

(R)-MOPn

PPh2 OMe

O pro-S N H

R base (R)-MOP

Pd

Br achiral, with enantiotopic amide groups O

R

O

O

N (R)-MOPn

Pd

(R)

N H

R R

O

O

R

O

N N H

diastereomeric intermediates (formed unequally)

ACS PRF #49493-UR1

base • HBr

single enantiomer, with diastereotopic amide groups

(S)

Pd

(R)-MOPn

reductive elimination R

N

(R)

R R NH

HN

O (S)

O N

enantiomeric products in yields up to 99% and enantiomeric excesses up to 96%

R