Steric control of the in/out sense of bridgehead substituents in macrobicyclic compounds: isolation of new "crossed chain" variants of in/out isomers.
Isomers of the cage like dibridgehead diphosphine P((CH2)14)3P (1) are treated with Ph3PAu(2,6-C6H3(Trip)2) (2 equiv.; Trip = 2,4,6-C6H2(iPr)3). With out,out-1, workup gives out,out-1·(Au(2,6-C6H3(Trip)2))2 (46%), as confirmed by a crystal structure. With in,out-1, crystallization affords not in,out-1·(Au(2,6-C6H3(Trip)2))2, but rather an out,out isomer in which one of the (CH2)14 segments threads through the macrocycle formed by the other two. Implications for mechanisms of interconversion of in,out isomers are analyzed.
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA. Gladysz@mail.chem.tamu.edu.
Michael
M
Stollenz
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA. Gladysz@mail.chem.tamu.edu.
Deeb
D
Taher
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA. Gladysz@mail.chem.tamu.edu.
Nattamai
N
Bhuvanesh
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA. Gladysz@mail.chem.tamu.edu.
Joseph H
JH
Reibenspies
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA. Gladysz@mail.chem.tamu.edu.
Zuzana
Z
Baranová
Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station, Texas 77842-3012, USA. Gladysz@mail.chem.tamu.edu.
John A
JA
Gladysz