The synthesis and characterization of four new hemicarcerands (1-4) are reported, whose interiors in principle are large enough to embrace such guests as tetraphenylporphyrin or [60lfullerene.Prior publications report syntheses of hemicarcerands with large enough portals and interiors to allow guests like [3.3]paracyclophane to be incarcerated at temperatures of 120-220 "C to give hemicarceplexes stable towards decomplexation in solution at ambient temperatures.1 Mechanical inhibition of hemicarceplex decomplexation has been termed constrictive binding,2 which coupled with host-guest attractive forces accounts for the stability to chemical3 and physical2 manipulation of hemicarceplexes. This paper addresses the question of whether hemicarcerands can be prepared with large enough enforced interiors to incarcerate guests such as tetraphenylporphyrin or [60]fullerene (c60). A complex of the former might act as an oxidation catalyst stabilized by the shell, whereas the host of a capsular complex of c 6 0 should impart interesting new properties to that molecule. We have success- +

The syntheses, characterization (including a crystal structure determination), and limited constrictive binding properties of two octaamide hemicarcerands are reported, as well as a fourfold rearrangement of an acid-acetal to a phenol-lactone-acetal, the crystal structure of which has been determined. ~We previously reported the synthesis and constrictive binding properties of hydrolytically unstable hemicarcerands 11 and 22 with portals and enforced interiors large enough to admit and expel neutral guests at high temperatures, but which were stable at ambient temperature. We now report the syntheses and characterization of the hydrolytically more stable systems, 3 and 4, derived from 5-10, and the interesting rearrangement of the tetracarboxylic acid related to 8 to give 11.The syntheses of 3 and 4 were accomplished by the reaction sequences 53 + St + 91 -+ 31, and 63 -+ lot 3 4,T?-These new compounds all gave C, H and N (when present) within 0.30% of theory, Mmlz signals of substantial intensity, and lH and 13C NMR spectra consistent with their structures.

Ausgehend von höheren Olefinen (>C12) bietet die Rhodium‐katalysierte Hydroamino‐methylierung einen einstufigen und atomeffizienten Zugang zu Fettaminen. Unter optimierten Bedingungen können hohe Katalysatoraktivitäten und ‐produktivitäten erzielt werden und die linearen Produkte mit ausgezeichneter Regioselektivität erhalten werden.