Binap, (A+-)- → HCID 67278909, compound

HRID 1190050Notes

Reaction equation

HRID 1190050 reaction equation
[CH:1]([Si:4]([CH:24]([CH3:26])[CH3:25])([CH:21]([CH3:23])[CH3:22])[O:5][CH2:6][CH:7]([NH2:20])[CH2:8][O:9][Si:10]([CH:17]([CH3:19])[CH3:18])([CH:14]([CH3:16])[CH3:15])[CH:11]([CH3:13])[CH3:12])([CH3:3])[CH3:2].[CH3:27][O:28][C:29]([C:31]1[S:32][C:33]([C:37]2[CH2:42][CH2:41][C:40]([CH3:44])([CH3:43])[CH2:39][CH:38]=2)=[CH:34][C:35]=1Br)=[O:30].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCOCC1.C(Cl)Cl.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:27][O:28][C:29]([C:31]1[S:32][C:33]([C:37]2[CH2:42][CH2:41][C:40]([CH3:44])([CH3:43])[CH2:39][CH:38]=2)=[CH:34][C:35]=1[NH:20][CH:7]([CH2:8][O:9][Si:10]([CH:11]([CH3:13])[CH3:12])([CH:17]([CH3:19])[CH3:18])[CH:14]([CH3:16])[CH3:15])[CH2:6][O:5][Si:4]([CH:1]([CH3:3])[CH3:2])([CH:21]([CH3:23])[CH3:22])[CH:24]([CH3:26])[CH3:25])=[O:30]

Participants

7

Reactant 3

HCID 634876Binap, (A+-)-HCID 57795502HCID 57795502, compoundHCID 57945297HCID 57945297, compound

Product 1

HCID 67278909HCID 67278909, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 6344DichloromethaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

Nitrogen was bubbled through a mixture of 2-triisopropylsilanyloxy-1-triisopropylsilanyloxymethyl-ethylamine (prepared from serinol using triisopropylsilyl chloride) (420 mg, 1.04 mmol) and 3-bromo-5-(4,4-dimethyl-cyclohex-1-enyl)-thiophene-2-carboxylic acid methyl ester (350 mg, 1.06 mmol) in dioxane (3.5 mL) containing CS2CO3 (1 g, 3.07 mmol) and Pd2(dba)3 (96 mg, 0.1 mmol) for 6 min. 2,2′-Bis(diphenylphosphino)-1,1′-binaphthyl (105 mg, 0.17 mmol) was added and the mixture was stirred at 80° C. for 24 h. It was diluted with DCM, filtered through celite and evaporated. 5-(4,4-Dimethyl-cyclohex-1-enyl)-3-(2-triisopropylsilanyloxy-1-triisopropylsilanyloxymethyl-ethylamino)-thiophene-2-carboxylic acid methyl ester was obtained by chromatography over silica gel (hexane:EtOAc-95:5) (500 mg, 72%).

Workup

  1. filtrationfiltered through celite
  2. customevaporated

Sources & evidence

ORD record
ord-dc02b7ad84d249d8bfd7ce7996a66d32
Source dataset
uspto-grants-2014_03
Patent number
US08674118B2

Reaction notes

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