Our new synthetic strategy had enabled us to prepare five distinct diazabicyclic bridged amides (and substituted/fused variants) varying systematically in the size of each ring, enabling interrogation of the impact on molecular properties (Figure ; data for 'parent' scaffolds shown, for all data see Supporting Information). The reduced contribution from resonance forms with C=N character manifests itself in a greater degree of electron-deficiency at the carbonyl carbon, and hence higher Single crystal X-ray analysis of compound 6l also permits comparison with our previously reported structures of the N-Bn analogues of 6f/k. The significant pyramidalisation at nitrogen can be seen as a sum of the bond angles at that atom: while the Amide distortion can also be measured through the Winkler-Dunitz parameters: for example, the 'twist angle' τ (0 o for a planar amide and 90 o for a perpendicular arrangement) varies from 3.6-23.5 o across the series (for additional parameters, see Supporting Information). Finally, as expected, the N-C bond shortens with increased conjugation of the nitrogen lone pair: the relatively long bond of 1.380 Å in the N-Bn analogue of 6f shortens to 1.355 Å in 6l (cf. 1.475 Å in the most-twisted amide 1 4a and 1.325 Å for Nmethylpiperidone 4b ). We considered that the twist-induced destabilisation of (particularly) the smaller diazabicycles could make them competent acylating agents and hence they might have the potential to act as anti-microbial agents. Screening of a panel of compounds 6 was therefore carried out against Staphylococcus Aureus ATCC29213, with the strained tricyclic structure 6e showing activity at 32 µg/mL (see Supporting Information for full details). The modular nature of our synthetic approach meant that it could be readily adapted to the synthesis of related twisted anilines (Scheme 2). Hence, photoredox-catalysed hydroamination of enecarbamates 5a, c and e with 2-bromobenzylamine 10a followed by suitable amine protection gave adducts 11a-d. Removal of the Boc-group was followed by intramolecular amine arylation under Buchwald-Hartwig conditions, giving the desired homologous diazabicycles 7a-d. We also attempted to investigate homologues in the diazacyclic ring, but although the desired cyclisation precursor 11e could be readily prepared by reaction of 5c with 2-(2bromophenyl)ethan-1-amine 10b, the Buchwald-Hartwig cyclisation gave only a trace amount of the desired product 7e, reflecting the challenging nature of medium-ring formation. Scheme 2. Modular synthesis of twisted bicyclic anilines. i) [Ir(dF(Me)ppy) 2 (dtbbpy)PF 6 ] (2 mol%), TRIP thiol (50 mol%), toluene, blue LEDs; ii) CbzCl, NaHCO 3 , DCM; iii) TsCl, DIPEA, DMAP (5 mol%), DCM; iv) 6M HCl, EtOAc; v) Pd 2 (dba) 3 (4 mol%), BINAP (8 mol%), NaOtBu, toluene, reflux; vi) Pd(OAc) 2 (10 mol%), BINAP (20 mol%), Cs 2 CO 3 , toluene, reflux. Yields shown for steps from 11 to 7 (steps iv plus v/vi) only: for full details see Supporting Information.