Summary of test reaction conditions.
| Reaction | Temperature | Reagent 1 | Reagent 2 | Noted |
|---|---|---|---|---|
| 1i-ii | 40 | EDAC | HOBt | Two reactions at 1.0 and 1.5 eq. |
| 1iii-iv | 40 | HATU, 1.5 eq. | DIPEA, 3.0 eq. | Two reactions, add acid v. amine first |
| 1v-vi | 40 | CDI, 1.0 eq. | DIPEA, 3.0 eq.a | Two reactions, add acid v. amine first |
| 1vii | 40 | SOCl2, 1.5 eq. | DIPEA, 3.0 eq. | |
| 2i-iii | 80 | KOtBu, 3.0 eq. | Pd catalystsb | |
| 3i-iii | 80 | CuI, 0.2 eq. | DBU, DBU, Cs2CO3, 3.0 eq. | TBAB, aliquat 336, no PTC |
| 4i | 40 | EDAC | HOBt | Two reactions at 1.0 and 1.5 eq. |
| 4ii-iii | 40 | HATU, 1.5 eq. | DIPEA, 3.0 eq. | Two reactions, add acid v. amine first |
| 4iv-v | 40 | CDI, 1.0 eq. | DIPEA, 3.0 eq.a | Two reactions, add acid v. amine first |
| 5i-v | 80 | Basesc, 3.0 eq. | Five different bases and eq. | |
| 5vi-viii | 40 | EDAC | HOBt | Two reactions at 1.0 eq., one at 1.5 eq. |
| 5viv | 40 | PPh3, 1.0 eq. | DIAD, 1.2 eq.a | |
| 5x-xi | 40 | CDI, 1.0 eq. | DIPEA, 3.0 eq.a | Two reactions, add acid v. amine first |
| 5xii-xiii | 40 | SOCl2 | DIPEA, 3.0 eq. | Two reactions at 1.0 and 1.5 eq. SOCl2 |
| 6i-xi | 80 | DIPEA | F-, Cl-, and Br-nitropyridine | DIPEA at 1, 2, 3, and 4 eq. each X-pyr |
| 6xii-xiii | 80 | DBU, 3 eq. | Pd catalystsb | |
| 6xiv-xvii | 40 | SnCl2 | HCl | At 1.0, 2.0, 5.0, and 10.0 eq. |
| 6xviii-xxi | 40 | EDAC | HOBt | Two reactions at 1.0, third at 1.5 eq. |
| 6xxii-xxiv | 40 | HATU, 1.5 eq. | DIPEA, 3.0 eq. | Two reactions, add acid v. amine first |
| 6xxv-xxvi | 40 | CDI, 1.0 eq. | DIPEA, 3.0 eq.a | Two reactions, add acid v. amine first |
| 6xxvii | 40 | SOCl2 | DIPEA, 3.0 eq. | Two reactions at 1.0 and 1.5 eq. SOCl2 |
Reagent added last.
Palladium catalysts, in order: XPhos Pd G4, tBuBrettPhos Pd G3, (dppf)PdCl2.
Bases, in order, DIPEA, Cs2CO3, KOtBu, DBU, DBU (1.5 eq.).
Abbreviations. EDAC: 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, HOBt: N-hydroxybenzotriazole, HATU: 2-(7-aza-1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexafluorophosphate, DIPEA: diisopropyl ethyl amine, DIAD: diisopropylazodicarboxylate, DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene, KOtBu: potassium tert-butoxide, TBAB: tetrabutylammonium bromide, CDI: carbonyl diimidazole, SOCl2: thionyl chloride, CuI: copper(i) iodide, PPh3: triphenylphosphine, PTC: phase transfer catalyst, X-pyr: halogenated nitropyridine.