{"schemaVersion":1,"kind":"mol2mat-public-reaction-record","experiment":{"reaction_id":"ord-e5c44ec1b5164f8ea077cf3b7ee0214a","dataset_id":"ord_dataset-5540e162c09f4c04905ddc8ba9c931c6","reaction_class":"Copper-catalyzed hydroamination preparation","transformation_sha256":"1e11cc7f4f9c4e9a3ebdb3c2c60521ca8c45d8d66a93a6eae2b476968c949b6f","doi":"10.15227/orgsyn.095.0080","dataset_source_slug":"ord-dataset-5540e162c09f4c04905ddc8ba9c931c6","publication_source_slug":"ord-publication-8e01167d3a33166e","route_slugs":["ord-e5c44ec1b5164f8ea077cf3b7ee0214a-6d1104c6cb7f","ord-e5c44ec1b5164f8ea077cf3b7ee0214a-ed26d46e5c76"],"reactant_slugs":["ord-compound-e33cb85f3ffdaf6b4731","ord-compound-c48538141f742d70e0c0"],"product_slugs":["ord-compound-3c5ac9dc425b126d09a4"],"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":74,"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":9.09,"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":25,"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":5.41,"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"},"addition_device":{"type":"SYRINGE"}},"2,3,3-trimethyl-1-butene":{"components":[{"identifiers":[{"type":"SMILES","value":"CC(=C)C(C)(C)C"},{"type":"NAME","value":"2,3,3-trimethyl-1-butene"}],"amount":{"mass":{"value":2.5,"units":"GRAM"}},"reaction_role":"REACTANT","is_limiting":true,"preparations":[{"type":"NONE","details":"used as received (98% purity)"}],"source":{"vendor":"Sigma-Aldrich"}}],"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":330,"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":46,"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":"OIL_BATH"},"setpoint":{"value":40,"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":"TEMPERATURE","temperature":{"setpoint":{"value":23,"units":"CELSIUS"}}},{"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 using a 250-mL separatory funnel","keep_phase":"organic"},{"type":"CONCENTRATION","details":"rotary evaporator (35 degC, 50 mmHg)"},{"type":"FLASH_CHROMATOGRAPHY","details":"Silica (30 g) is added to the crude reaction mixture \nand the solvent removed in vacuo. This mixture is loaded onto a column, \nwith interior diameter of roughly 2 inches, packed with silica (200 g, \nSiliCycle, F60/230-400 mesh) and equilibrated with hexanes. The column is \neluted under air pressure with 1% ethyl acetate in hexanes (2500 mL). During \nelution, fractions are collected in test tubes (roughly 28 mL each), and the \ndesired product typically elutes around fractions 13 through 72 \n(Rf = 0.34). The fractions that contain the product are combined."},{"type":"CONCENTRATION","details":"rotary evaporator (30 degC, 80 mmHg)"}],"outcomes":[{"reaction_time":{"value":12,"units":"HOUR"},"products":[{"identifiers":[{"type":"SMILES","value":"C[C@@H](CN(CC1=CC=CC=C1)CC2=CC=CC=C2)C(C)(C)C"},{"type":"NAME","value":"(R)-N,N-Dibenzyl-2,3,3-trimethylbutan-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":87}},{"analysis_key":"quantitative NMR","type":"PURITY","percentage":{"value":97}},{"analysis_key":"chiral SFC","type":"SELECTIVITY","percentage":{"value":90},"selectivity":{"type":"EE"}},{"analysis_key":"isolated_weight","type":"AMOUNT","amount":{"mass":{"value":6.54,"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":296.2373},"found":{"float_value":296.2375}}},"isolated_weight":{"type":"WEIGHT","details":"6.54 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":"13.9, 27.6, 32.4, 41.0, 56.6, 59.1, 126.8, 128.2, 129.0, 140.2"}}},"thin film IR":{"type":"IR","details":"neat film, NaCl","is_of_isolated_species":true,"data":{"peaks":{"string_value":"3063, 3027, 2964, 2870, 2791, 1602, 1494, 1453, 1365, 1244, 1121, 1069, 1028, 974, 745, 698 cm-1"}}},"chiral SFC":{"type":"SFC","details":"FC (Daicel Chiralpak AD-H column, heated to 40 °C), eluting with a linear gradient over 6 min from 5% to 10% isopropanol in supercritical CO2 at 2.5 mL/min.: 2.57 min (major), 2.98 min (minor), 90% ee for both runs","is_of_isolated_species":true},"1H NMR":{"type":"NMR_1H","details":"400 MHz, CDCl3","is_of_isolated_species":true,"data":{"peaks":{"string_value":"0.81 (s, 9H), 0.90 (d, J = 6.7 Hz, 3H), 1.49 (dq, J = 7.1, 3.4 Hz, 1H), 2.13 (dd, J = 12.3, 10.5 Hz, 1H), 2.39 (dd, J = 12.2, 2.8 Hz, 1H), 3.21 (d, J = 13.7 Hz, 2H), 3.83 (d, J = 13.7 Hz, 2H), 7.23 (t, J = 7.3 Hz, 2H), 7.31 (t, J = 7.4 Hz, 4H), 7.37 (d, J = 7.5 Hz, 4H)"}}},"specific rotation":{"type":"CD","details":"Specific rotation: [α]D = -114 (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-e33cb85f3ffdaf6b4731","name":"2,3,3-trimethyl-1-butene","smiles":"C=C(C)C(C)(C)C","inchi":"InChI=1S/C7H14/c1-6(2)7(3,4)5/h1H2,2-5H3","formula":"C7H14"},{"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-3c5ac9dc425b126d09a4","name":"(R)-N,N-Dibenzyl-2,3,3-trimethylbutan-1-amine","smiles":"C[C@@H](CN(Cc1ccccc1)Cc1ccccc1)C(C)(C)C","inchi":"InChI=1S/C21H29N/c1-18(21(2,3)4)15-22(16-19-11-7-5-8-12-19)17-20-13-9-6-10-14-20/h5-14,18H,15-17H2,1-4H3/t18-/m0/s1","formula":"C21H29N"}],"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"]}