Lithium tri-s-butylborohydride → 1-Allyl-1,3,3a,4,5,6,6a,12a-octahydro-7,13-dioxo-1,5-methano-furo[3,4-d]xanthene

HRID 734183Notes

Reaction equation

HRID 734183 reaction equation
[CH2:1]([C:4]12[C:22](=[O:23])[CH:9]3[CH:10]=[C:11]4[C:20]1([CH:7]([CH2:8]3)[CH2:6][O:5]2)[O:19][C:18]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:12]4=[O:21])[CH:2]=[CH2:3].CCC(C)[BH-](C(C)CC)C(C)CC.[Li+]>O1CCCC1>[CH2:1]([C:4]12[C:22](=[O:23])[CH:9]3[CH2:10][CH:11]4[C:20]1([CH:7]([CH2:8]3)[CH2:6][O:5]2)[O:19][C:18]1[CH:17]=[CH:16][CH:15]=[CH:14][C:13]=1[C:12]4=[O:21])[CH:2]=[CH2:3]

Participants

4

Reactant 2

HCID 3611392Lithium tri-s-butylborohydrideHCID 112668131-Allyl-1,3,3a,4,5,12a-hexahydro-7,13-dioxo-1,5-methano-furo[3,4-d]xanthene

Product 1

HCID 578417471-Allyl-1,3,3a,4,5,6,6a,12a-octahydro-7,13-dioxo-1,5-methano-furo[3,4-d]xantheneYield 39%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a stirring solution of 1-allyl-1,3,3a,4,5,12a-hexahydro-7,13-dioxo-1,5-methano-furo[3,4-d]xanthene (29.0 mg, 0.0941 mmol) and tetrahydrofuran (15.0 mL) in a dry ice bath under argon was added dropwise 1.0 M L-Selectride in THF (150 μL, 0.150 mmol) and the solution was stirred for 25 min. The dry ice bath was removed and the solution was stirred for 20 minutes. The solution was concentrated by rotary evaporation and was purified by column chromatography (2:1 hexanes/ethyl acetate) to yield 11.4 mg (39%) of the title compound as a white solid. 1H NMR (CDCl3, 300 MHz): δ 7.91 (dd, J1=8.11 Hz, J2=1.79, 1H), 7.54 (ddd, J1=8.17 Hz, J2=6.94, J3=1.45, 1H), 7.08 (m, 2H), 5.86 (m, 1H), 5.27 (m, 1H), 5.12 (dt, J1=10.16 Hz, J2=1.51, 1H), 4.16 (dd, J1=7.97 Hz, J2=4.12, 1H), 3.53 (d, J=7.96 Hz, 1H), 3.40 (dd, J1=11.54 Hz, J2=3.30, 1H), 3.06 (dd, J1=13.46 Hz, J2=6.04, 1H), 2.87 (dd, J1=13.32 Hz, J2=8.93, 1H), 2.82 (dt, J1=14.28 Hz, J2=3.57, 1H), 2.74 (dd, J1=9.89 Hz, J2=4.39, 1H), 2.44 (m, 1H), 2.01 (dd, J1=13.47 Hz, J2=10.44, 1H), 1.78 (ddt, J1=14.15 Hz, J2=11.67 J3=2.68, 1H), 1.67 (dt, J1=14.10 Hz, J2=3.50, 1H).

Workup

  1. customThe dry ice bath was removed
  2. stirringthe solution was stirred for 20 minutes
  3. concentrationThe solution was concentrated by rotary evaporation
  4. customwas purified by column chromatography (2:1 hexanes/ethyl acetate)

Sources & evidence

ORD record
ord-f10bf4e9c94743258c2b4d44bb870192
Source dataset
uspto-grants-2009_09
Patent number
US07592143B2

Reaction notes

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