Participants
| Role | Name | HCID | Charge |
|---|
| Reactant | Water | HCID 962 | — |
| Reactant | 1,2-Dibromoethane | HCID 7839 | — |
| Reactant | Tert-butyl 3-iodoazetidine-1-carboxylate | HCID 11000522 | — |
| Reactant | HCID 46870536 | HCID 46870536 | — |
| Catalyst | Zinc | HCID 23994 | — |
| Catalyst | Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI) | HCID 24350 | — |
| Catalyst | Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+) | HCID 178418228 | — |
| Solvent | Dimethylacetamide | HCID 31374 | — |
| Product | HCID 57476712 | HCID 57476712 | 86.3% |
Reaction Steps
A suspension of zinc powder (152 mg, 2.3 mmol) in 1 ml of DMA in a dry flask was heated under N2 to 65-70° C. A mixture of TMS-CI (28 mg, 0.26 mmol) and 1,2-dibromoethane (49 mg, 0.26 mmol) was added dropwise, stirred for 30 min, followed by slow (15 min) addition of 3-iodo-azetidine-1-carboxylic acid tert-butyl ester (510 mg, 1.8 mmol) in 1 ml DMA. The reaction was cooled slowly (3 h) to room temperature, added to a mixture of 8-(3,4-chlorobenzyl)-7-[(ethoxycarbonyl)amino)-5,6,7,8-tetrahydronaphthalen-2-yl trifluoromethanesulfonate (633 mg, 1.3 mmol, prepared in analogy to example 29), CuI (74 mg, 0.39 mmol) and PdCl2(dppf) (63 mg, 0.08 mmol) in 4 ml DMA preheated to 70° C. and stirred for 7 h at 70° C. Water and MTB (1:1 20 ml) were added and the resulting mixture filtered. The organic layer was separated, dried (Na2SO4) and the solvent evaporated. Purification by chromatography afforded 560 mg of product (white foam).
Provenance & Evidence
| DOI | 10.6084/m9.figshare.5104873.v1 |
|---|
| Patent number | US08563617B2 |
|---|
| Source dataset | uspto-grants-2013_10 |
|---|
| ORD ID | ord-b013d68bcc324860b7d206d6a5061479 |
|---|
| Source note | uspto-grants-2013_10 |
|---|
