1,1-Diphenylethylene → HCID 86720728, compound

HRID 873506Notes

Reaction equation

HRID 873506 reaction equation
[C:1]1([C:7]([C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)=[CH2:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[N+](=[C:17]([C:22]1[CH:31]=[CH:30][C:29]2[C:24](=[CH:25][CH:26]=[CH:27][CH:28]=2)[CH:23]=1)[C:18]([O:20][CH3:21])=[O:19])=[N-]>CCCCCCCCCCCCC1C=CC(S(N2[C@@H](C(O)=O)CCC2)(=O)=O)=CC=1.CCCCCCCCCCCCC1C=CC(S(N2[C@@H](C(O)=O)CCC2)(=O)=O)=CC=1.CCCCCCCCCCCCC1C=CC(S(N2[C@@H](C(O)=O)CCC2)(=O)=O)=CC=1.CCCCCCCCCCCCC1C=CC(S(N2[C@@H](C(O)=O)CCC2)(=O)=O)=CC=1.[Rh].[Rh]>[CH:23]1[C:24]2[C:29](=[CH:28][CH:27]=[CH:26][CH:25]=2)[CH:30]=[CH:31][C:22]=1[C@:17]1([C:18]([O:20][CH3:21])=[O:19])[CH2:8][C:7]1([C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1

Participants

4

Reactant 2

HCID 107401,1-DiphenylethyleneHCID 73196574HCID 73196574, compound

Product 1

HCID 86720728HCID 86720728, compoundYield 74%

Reagents, catalysts & solvents 1

HCID 11007799Tetrakis[(R)-(+)-N-(p-dodecylphenylsulfonyl)prolinato]dirhodium(II)Catalyst

Procedure

To a flame-dried round bottom flask kept under a dry atmosphere of argon, was added Rh2(R-DOSP)4 (0.01 equiv., 474 mg), 1,1-diphenylethlyene (2.32 equiv., 10.5 g, 58 mmol), and dry degassed pentane (100 mL). A solution of freshly prepared methyl 2-diazo-2-(naphthalen-2-yl)acetate (1.0 equiv., 5.65 g, 25 mmol) in dry, degassed pentane (250 mL) was added to the former solution drop-wise over 3 hours at −40° C. The mixture was allowed to stir overnight to room temperature, and then concentrated in vacuo. The crude material was purified using flash column chromatography eluting with a 40:1 mixture of hexanes/ethyl acetate to provide the desired product as a white solid (7.0 g, 74% yield, >99% ee). mp: 138-139° C.; [α]20D −347.9° (c=1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.78 (s, 1H), 7.74-7.71 (m, 1H), 7.50-7.36 (m, 4H), 7.24-7.22 (m, 1H), 7.06-7.04 (m, 2H), 6.96-6.86 (m, 3H), 3.38 (s, 3H), 2.79 (d, J=5.6 Hz, 1H), 2.57 (d, J=5.6 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 171.4, 141.9, 139.4, 133.6, 132.8, 132.3, 130.4, 130.2, 129.9, 128.7, 128.3, 127.7, 127.6, 127.5, 126.9, 126.7, 126.1, 125.8, 125.6, 141.9, 139.4, 133.6, 132.8, 132.2, 130.4, 130.2, 129.9, 128.7, 128.3, 127.7, 127.6, 127.5, 126.9, 126.7, 126.1, 125.8, 125.6, 52.2, 44.5, 43.2, 23.1; IR (neat): 3057, 3024, 2947, 1724, 1433, 1215; HRMS (APCI) calcd for C27H23O2 (M+H)+ 379.16926. found 379.16952; HPLC (ODH, 0.5% isopropanol in hexane, 1.0 mL/min, 1 mg/mL, 30 min, UV 254 nm) retention times of 8.6 min (major) and 9.6 min (minor), >99% ee.

Workup

  1. customTo a flame-dried round bottom flask kept under a dry atmosphere of argon
  2. customdry
  3. customdegassed pentane (100 mL)
  4. customdegassed pentane (250 mL)
  5. additionwas added to the former solution drop-wise over 3 hours at −40° C
  6. concentrationconcentrated in vacuo
  7. customThe crude material was purified
  8. washeluting with a 40:1 mixture of hexanes/ethyl acetate

Sources & evidence

ORD record
ord-b5e01c3bd8b54975b7ca1ce06c4a8b99
Source dataset
uspto-grants-2015_03
Patent number
US08975428B2

Reaction notes

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