Carbon Dioxide → HCID 21844652, compound

HRID 1738623Notes

Reaction equation

[O-]P(OP([O-])[O-])[O-].CC(C1C=[C:16]([O:18]C)[CH:15]=[C:14]([C:20]2[C:25]([O:26]P3OC4C(=CC=CC=4)C4C(=CC=CC=4)O3)=[C:24](C(C)(C)C)[CH:23]=[C:22](OC)[CH:21]=2)C=1OP1OC2C(=CC=CC=2)C2C(=CC=CC=2)O1)(C)C.C=CCC([OH:71])CC=C.C(=O)=O>>[CH:21]([CH2:22][CH2:23][CH2:24][CH:25]1[O:26][CH:16]([OH:18])[CH2:15][CH2:14][CH2:20]1)=[O:71]

Participants

Reactant 4

HCID 280Carbon Dioxide

HCID 17902Hepta-1,6-dien-4-ol

HCID 108658296,6′-[[3,3′-Bis(1,1-dimethylethyl)-5,5′-dimethoxy[1,1′-biphenyl]-2,2′-diyl]bis(oxy)]bis[dibenzo[d,f][1,3,2]dioxaphosphepin]

HCID 22239282Diphosphite

Product 1

HCID 21844652HCID 21844652, compound

Conditions

Temperature: -60 °C

Procedure

To a 300 mL stainless steel autoclave with two sapphire windows containing Rh(acac)(CO)2 (1.5 mg, 6×10-3 mmol) and a diphosphite ligand, BIPHEPHOS or MCP-1, (1.2×10-2 mmol) was added 1,6-heptadien-4-ol (112 mg, 1.0 mmol). The air was replaced by CO and CO (7 atm) was introduced followed by H2 (7 atm). The reaction vessel was cooled to -60° C. and CO2 (85 atm) was introduced. The mixture was allowed to stir at 65° C. and 100 atm overnight. The autoclave was cooled to 0° C. and all the gasses were carefully released. The reaction mixture was then concentrated under vacuum and the residue was chromatographed on silica gel using hexane/AcOEt as the eluant to give 6-(3-formylpropyl)-2-hydroxytetrahydropyran in nearly quantitative yield: 1H NMR (CDCl3) (two diastereomers) δ 1.14-2.02 (m, 10 H), 2.43 (t, J=6.8 Hz, 2 H), 3.16 (br s, 1 H), [3.36-3.44 (m), 3.88-3.96 (m)] (1 H), [4.66 (d, J=9.1 Hz), 5.26 (br s)] (1 H), 9.74 (s, 1 H); 13C NMR (CDCl3) δ [17.50, 18.04], 21.95, [30.26, 30.99], [32.55, 32.03], [35.01, 35.18], [43.13, 43.52], [72.96, 75.64], [91.36, 96.21], [201.90, 202.74]; IR (neat, cm-1) 3420, 2942, 2867, 2723, 1724, 1458, 1440, 1412, 1390, 1352, 1184, 1116, 1066, 1035, 977.

Workup

additionwas introduced
custom100 atm overnight
temperatureThe autoclave was cooled to 0° C.
concentrationThe reaction mixture was then concentrated under vacuum
customthe residue was chromatographed on silica gel

Sources & evidence

ORD record: ord-393e902bfd124c53a0df5e372df3975b
Source dataset: uspto-grants-1999_10
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05962744

Reaction notes

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