Reaction discovery employing macrocycles: transannular cyclizations of macrocyclic bis-lactams.
Macrocyclic bis-lactams have been synthesized by cyclodimerization of homoallylic amino esters employing a Zr(IV)-catalyzed ester-amide exchange protocol. Base-mediated transannular cyclizations have been identified to access both bicyclic [5-11] and tricyclic [5-8-5] frameworks in good yield and diastereoselectivity. Preliminary mechanistic studies support an olefin isomerization-intramolecular conjugate addition pathway.
Han
Chong
C
Department of Chemistry and Center for Chemical Methodology and Library Development, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215, USA.
Rangarajan
Sathish
S
Voukides
Alicia C
AC
Beeler
Aaron B
AB
Johnson
Richard
R
Porco
John A
JA
D003500:Cyclization; D007700:Kinetics; D007769:Lactams / Q000737:chemistry*; D047028:Macrocyclic Compounds / Q000737:chemistry*; D008958:Models, Molecular; D008968:Molecular Conformation; D013237:Stereoisomerism
D007769:Lactams; D047028:Macrocyclic Compounds