{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-7b927700e3414788865b46a4d4b18c44","dataset_id":"ord_dataset-5540e162c09f4c04905ddc8ba9c931c6","reaction_class":"Copper-catalyzed hydroamination preparation","transformation_sha256":"c535a2c8bcc008f9a4adf022534429a78f41de771eedabfa00c8f3f39856d1fc","doi":"10.15227/orgsyn.095.0080","dataset_source_slug":"ord-dataset-5540e162c09f4c04905ddc8ba9c931c6","publication_source_slug":"ord-publication-8e01167d3a33166e","route_slugs":["ord-7b927700e3414788865b46a4d4b18c44-15e5d365fe11","ord-7b927700e3414788865b46a4d4b18c44-7a03afaff6ba"],"reactant_slugs":["ord-compound-c48538141f742d70e0c0","ord-compound-f26520290a99e5f2db32"],"product_slugs":["ord-compound-c5a650022dc53dd8be16"],"selection_notes":["Only explicitly marked REACTANT inputs become graph starting points.","Only products with a positive reported numeric YIELD become graph destinations; all reported outcomes remain in raw.","One representative record per exact reactant/product structure set; other conditions are not additional transformations."],"raw":{"inputs":{"triphenylphosphine":{"components":[{"identifiers":[{"type":"SMILES","value":"c3c(P(c1ccccc1)c2ccccc2)cccc3"},{"type":"NAME","value":"triphenylphosphine"}],"amount":{"mass":{"value":61,"units":"MILLIGRAM"}},"reaction_role":"CATALYST","preparations":[{"type":"NONE","details":"used as received (99% purity)"}],"source":{"vendor":"Sigma-Aldrich"}}],"addition_order":4},"N,N-Dibenzyl-O-pivaloylhydroxylamine":{"components":[{"identifiers":[{"type":"SMILES","value":"O=C(C(C)(C)C)ON(CC1=CC=CC=C1)CC2=CC=CC=C2"},{"type":"NAME","value":"N,N-Dibenzyl-O-pivaloylhydroxylamine"}],"amount":{"mass":{"value":7.55,"units":"GRAM"}},"reaction_role":"REACTANT","is_limiting":false,"preparations":[{"type":"SYNTHESIZED","reaction_id":"ord-352807a1f4c14595afeef50c6c39ae38"}]}],"addition_order":1},"THF":{"components":[{"identifiers":[{"type":"SMILES","value":"C1CCOC1"},{"type":"NAME","value":"THF"}],"amount":{"volume":{"value":21,"units":"MILLILITER"}},"reaction_role":"SOLVENT","preparations":[{"type":"DRIED","details":"purified by passage under argon pressure through two packed columns of neutral alumina and copper(II) oxide"}],"source":{"vendor":"J. T. Baker"}}],"addition_order":6,"addition_device":{"type":"SYRINGE"}},"dimethoxy(methyl)silane":{"components":[{"identifiers":[{"type":"SMILES","value":"CO[Si](C)OC"},{"type":"NAME","value":"dimethoxy(methyl)silane"}],"amount":{"mass":{"value":4.49,"units":"GRAM"}},"reaction_role":"REAGENT","preparations":[{"type":"NONE","details":"used as received (>97% purity, stored at -20 C)"}],"source":{"vendor":"TCI America"}}],"addition_order":7,"addition_speed":{"type":"DROPWISE"},"addition_duration":{"value":10,"units":"MINUTE"}},"trans-β-methylstyrene":{"components":[{"identifiers":[{"type":"SMILES","value":"C/C=C/C1=CC=CC=C1"},{"type":"NAME","value":"trans-β-methylstyrene"}],"amount":{"mass":{"value":2.5,"units":"GRAM"}},"reaction_role":"REACTANT","is_limiting":true,"preparations":[{"type":"NONE","details":"used as received (97% purity, stabilized)"}],"source":{"vendor":"Combi-Blocks or Acros"}}],"addition_order":5},"(S)-DTBM-SEGPHOS":{"components":[{"identifiers":[{"type":"SMILES","value":"CC(C)(C)C1=CC(=CC(=C1OC)C(C)(C)C)P(C2=C(C3=C(C=C2)OCO3)C4=C(C=CC5=C4OCO5)P(C6=CC(=C(C(=C6)C(C)(C)C)OC)C(C)(C)C)C7=CC(=C(C(=C7)C(C)(C)C)OC)C(C)(C)C)C8=CC(=C(C(=C8)C(C)(C)C)OC)C(C)(C)C"},{"type":"NAME","value":"(S)-DTBM-SEGPHOS"}],"amount":{"mass":{"value":274,"units":"MILLIGRAM"}},"reaction_role":"CATALYST","preparations":[{"type":"NONE","details":"used as received (>94% purity)"}],"source":{"vendor":"Takasago"}}],"addition_order":3},"copper(II) acetate":{"components":[{"identifiers":[{"type":"SMILES","value":"CC(=O)[O-].CC(=O)[O-].[Cu+2]"},{"type":"NAME","value":"copper(II) acetate"}],"amount":{"mass":{"value":38,"units":"MILLIGRAM"}},"reaction_role":"CATALYST","preparations":[{"type":"NONE","details":"used as received (97% purity)"}],"source":{"vendor":"Strem"}}],"addition_order":2}},"setup":{"vessel":{"type":"ROUND_BOTTOM_FLASK","details":"two-necked","material":{"type":"GLASS"},"preparations":[{"type":"OVEN_DRIED"},{"type":"PURGED","details":"with nitrogen"}],"attachments":[{"type":"SEPTUM","details":"rubber"},{"type":"SEPTUM","details":"rubber"}],"volume":{"value":250,"units":"MILLILITER"}},"is_automated":false,"environment":{"type":"FUME_HOOD"}},"conditions":{"temperature":{"control":{"type":"WATER_BATH","details":"removed from water bath after 10 min for 12 hour duration"},"setpoint":{"value":23,"units":"CELSIUS"}},"pressure":{"control":{"type":"SLIGHT_POSITIVE","details":"sealed with rubber septum, pierced with needle connected to manifold"},"atmosphere":{"type":"NITROGEN","details":"dry nitrogen"}},"stirring":{"type":"STIR_BAR"},"conditions_are_dynamic":true,"details":"After dropwise addition of dimethoxy(methyl)-\nsilane into reaction mixture in water bath, the vessel was removed and allowed\nto stir for an additional 12 hours"},"observations":[{"time":{"value":0,"units":"MINUTE"},"comment":"blue"},{"time":{"value":10,"units":"MINUTE"},"comment":"orange"}],"workups":[{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"O"},{"type":"NAME","value":"water"}],"amount":{"volume":{"value":50,"units":"MILLILITER"},"volume_includes_solutes":true}},{"identifiers":[{"type":"SMILES","value":"[Na+].OC([O-])=O"},{"type":"NAME","value":"sodium bicarbonate"}],"amount":{"mass":{"value":5,"units":"GRAM"}}}]}},{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"O=C(OCC)C"},{"type":"NAME","value":"EtOAc"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"O=C(OCC)C"},{"type":"NAME","value":"EtOAc"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"ADDITION","input":{"components":[{"identifiers":[{"type":"SMILES","value":"O=C(OCC)C"},{"type":"NAME","value":"EtOAc"}],"amount":{"volume":{"value":50,"units":"MILLILITER"}}}]}},{"type":"EXTRACTION","details":"3 x 50 mL ethyl acetate extraction","keep_phase":"organic"},{"type":"CONCENTRATION","details":"rotary evaporator (35 degC, 50 mmHg)"},{"type":"FLASH_CHROMATOGRAPHY","details":"The crude reaction mixture is dissolved in a minimal quantity of \nbenzene or toluene and is loaded onto a column, with interior diameter of roughly 2 \ninches, packed with silica (200 g, SiliCycle, F60/230-400 mesh) and equilibrated with \nhexanes. The column is eluted under air pressure with hexanes (500 mL), then 1% ethyl \nacetate in hexanes (1 L), then 2% ethyl acetate in hexanes (1 L). During elution, \nfractions are collected in test tubes (roughly 28 mL each), and the desired product \ntypically elutes around fractions 18 through 66. The fractions that contain the \nproductare combined"},{"type":"CONCENTRATION","details":"rotary evaporator (30 degC, 80 mmHg)"}],"outcomes":[{"reaction_time":{"value":12,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"CC[C@@H](N(CC1=CC=CC=C1)CC2=CC=CC=C2)C3=CC=CC=C3"},{"type":"NAME","value":"(R)-N,N-Dibenzyl-1-phenylpropan-1-amine"}],"is_desired_product":true,"measurements":[{"analysis_key":"1H NMR","type":"IDENTITY"},{"analysis_key":"13C NMR","type":"IDENTITY"},{"analysis_key":"HRMS","type":"IDENTITY"},{"analysis_key":"thin film IR","type":"IDENTITY"},{"analysis_key":"isolated_weight","type":"YIELD","percentage":{"value":86}},{"analysis_key":"quantitative NMR","type":"PURITY","percentage":{"value":99}},{"analysis_key":"chiral HPLC","type":"SELECTIVITY","percentage":{"value":99},"selectivity":{"type":"EE"}},{"analysis_key":"isolated_weight","type":"AMOUNT","amount":{"mass":{"value":5.72,"units":"GRAM"}}}],"isolated_color":"colorless","texture":{"type":"OIL"},"reaction_role":"PRODUCT"}],"analyses":{"HRMS":{"type":"HRMS","details":"ESI-TOF","is_of_isolated_species":true,"data":{"expected":{"float_value":316.206},"found":{"float_value":316.2049}}},"isolated_weight":{"type":"WEIGHT","details":"5.72 g recovered after workup","is_of_isolated_species":true},"13C NMR":{"type":"NMR_13C","details":"101 MHz, CDCl3","is_of_isolated_species":true,"data":{"peaks":{"string_value":"11.9, 24.4, 53.8, 63.8, 126.8, 127.0, 128.0, 128.3, 128.9, 129.1, 139.1, 140.6"}}},"thin film IR":{"type":"IR","details":"neat film, NaCl","is_of_isolated_species":true,"data":{"peaks":{"string_value":"3083, 3061, 3027, 2962, 2932, 2873, 2802, 1948, 1872, 1809, 1602, 1493, 1453, 761, 742 cm-1"}}},"1H NMR":{"type":"NMR_1H","details":"400 MHz, CDCl3","is_of_isolated_species":true,"data":{"peaks":{"string_value":"1.01 (t, J = 7.3 Hz, 3H), 1.89 (ddq, J = 14.2, 7.2, 7.1 Hz, 1H), 2.17 (ddq, J = 14.1, 7.2, 7.1 Hz, 1H), 3.24 (d, J = 13.9 Hz, 2H), 3.68 (t, J = 7.5 Hz, 1H), 3.91 (d, J = 13.8 Hz, 2H), 7.50-7.28 (m, 15H)"}}},"chiral HPLC":{"type":"LC","details":"HPLC (Daicel Chiralpak OD-H column), eluting with 4% isopropanol in hexanes at 0.6 mL/min: 10.9 min (minor), 13.4 min (major), 98% ee for the first run and 99% ee for the second run","is_of_isolated_species":true},"specific rotation":{"type":"CD","details":"Specific rotation: [α]D = +108 (c = 1.0, chloroform)","is_of_isolated_species":true},"quantitative NMR":{"type":"NMR_1H","details":"Quantitative NMR using ferrocene (98%, purchased from Sigma-Aldrich, recrystallized from pentane) in CDCl3","is_of_isolated_species":true}}}],"provenance":{"doi":"10.15227/orgsyn.095.0080","publication_url":"http://www.orgsyn.org/demo.aspx?prep=v95p0080"}}},"entities":[{"slug":"ord-compound-c48538141f742d70e0c0","name":"N,N-Dibenzyl-O-pivaloylhydroxylamine","smiles":"CC(C)(C)C(=O)ON(Cc1ccccc1)Cc1ccccc1","inchi":"InChI=1S/C19H23NO2/c1-19(2,3)18(21)22-20(14-16-10-6-4-7-11-16)15-17-12-8-5-9-13-17/h4-13H,14-15H2,1-3H3","formula":"C19H23NO2"},{"slug":"ord-compound-f26520290a99e5f2db32","name":"trans-β-methylstyrene","smiles":"C/C=C/c1ccccc1","inchi":"InChI=1S/C9H10/c1-2-6-9-7-4-3-5-8-9/h2-8H,1H3/b6-2+","formula":"C9H10"},{"slug":"ord-compound-c5a650022dc53dd8be16","name":"(R)-N,N-Dibenzyl-1-phenylpropan-1-amine","smiles":"CC[C@H](c1ccccc1)N(Cc1ccccc1)Cc1ccccc1","inchi":"InChI=1S/C23H25N/c1-2-23(22-16-10-5-11-17-22)24(18-20-12-6-3-7-13-20)19-21-14-8-4-9-15-21/h3-17,23H,2,18-19H2,1H3/t23-/m1/s1","formula":"C23H25N"}],"dataset":{"dataset_id":"ord_dataset-5540e162c09f4c04905ddc8ba9c931c6","name":"Copper-Catalyzed Enantioselective Hydroamination of Alkenes","description":"Reaction data from Org. Synth. 2018, 95, 80-96 (DOI: 10.15227/orgsyn.095.0080)","records_in_source":3,"path":"data/55/ord_dataset-5540e162c09f4c04905ddc8ba9c931c6.parquet","sha256":"7e44b014c9041d86e00bc4fb4b70b3c6b3b94c0e35634467ace02c330efcd1a4","bytes":13289,"repository_url":"https://github.com/open-reaction-database/ord-data/blob/83f971f586f6ad18f358ae4ae99d045e94ed2066/data/55/ord_dataset-5540e162c09f4c04905ddc8ba9c931c6.parquet","download_url":"https://huggingface.co/datasets/open-reaction-database/ord-data/resolve/93475c46949f9218e1dfb6624096025135db2add/data/55/ord_dataset-5540e162c09f4c04905ddc8ba9c931c6.parquet"},"publication":{"slug":"ord-publication-8e01167d3a33166e","title":"Literature experiment — 10.15227/orgsyn.095.0080","source_type":"paper","doi":"10.15227/orgsyn.095.0080","url":"https://doi.org/10.15227/orgsyn.095.0080","note":"Publication DOI reported by the Open Reaction Database. Experimental record data adapted under CC BY-SA 4.0; https://creativecommons.org/licenses/by-sa/4.0/"},"license":"CC-BY-SA-4.0","license_url":"https://creativecommons.org/licenses/by-sa/4.0/","attribution":"Open Reaction Database contributors and the cited original publications","changes":["Bounded selection across datasets and publications","Deduplicated exact transformations across conditions","Canonicalized molecular structures using RDKit; calculated identifiers, formulae and molecular weights","Explicitly incomplete directed branches for all recorded reactants and positively measured products","Removed submitter account and contact fields from provenance; retained scientific input and outcome fields"]}