Hydrogen bonding by chloroform-d as a conformational probe of the macrobicyclic diamines

Molecules that Turn Themselves Inside‐Out: Tuning in/out Equilibria and Homeomorphic Isomerization in Macrobicyclic Dibridgehead Diphosphines P((CH2)n)3P Newly Accessible by Earth‐Abundant‐Metal Templates

“…[2e] There is a more extensive, DuPont-derived literature of nitrogen analogs N((CH 2 ) n ) 3 N (6). [28][29][30] However, due to the low nitrogen inversion barriers, in/out isomers were inseparable, although an unassigned 1 H NMR decoalescence was observed for n = 8 and 10 below À 95 °C. [28,32] Syntheses have only been reported for n = 7-10 in the open literature, [28] but higher homologs were made available to external investigators (e. g., n = 12, 14) [29] and an extensive range was claimed in a patent (n = 15-22, 24, 28, 32, 34).…”

“…There is a more extensive, DuPont‐derived literature of nitrogen analogs N((CH 2 ) n ) 3 N ( 6 ) [28–30] . However, due to the low nitrogen inversion barriers, in / out isomers were inseparable, although an unassigned 1 H NMR decoalescence was observed for n =8 and 10 below −95 °C [28,32] .…”

“…However, due to the low nitrogen inversion barriers, in / out isomers were inseparable, although an unassigned 1 H NMR decoalescence was observed for n =8 and 10 below −95 °C [28,32] . Syntheses have only been reported for n =7–10 in the open literature, [28] but higher homologs were made available to external investigators (e. g., n =12, 14) [29] and an extensive range was claimed in a patent ( n =15–22, 24, 28, 32, 34) [31] . Key steps in the syntheses of these compounds are sketched in Scheme 6.…”