(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal → D-Arabitol

HRID 2050402Notes

Reaction equation

HRID 2050402 reaction equation
[O:1]=[CH:2][C@@H:3]([C@H:5]([C@@H:7]([C@@H:9](CO)[OH:10])[OH:8])[OH:6])[OH:4]>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh]>[CH2:2]([OH:1])[C@H:3]([C@@H:5]([C@@H:7]([CH2:9][OH:10])[OH:8])[OH:6])[OH:4]

Participants

3

Reactant 1

HCID 107526(2R,3S,4R,5R)-2,3,4,5,6-pentahydroxyhexanal

Product 1

HCID 94154D-ArabitolYield 88%

Reagents, catalysts & solvents 1

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)Catalyst

Procedure

Using the above described procedure of Example 1, glucose (Example 2) was cleanly decarbonylated by one equivalent of chlorotris(triphenylphosphine)rhodium to yield arabinitol (88%) in about 4 hours. Similarly, arabinose (Example 3) yielded erythritol (84%). Glyceraldehyde (Example 4), which has a higher free aldehyde content (ca. 2% in aqueous solution at room temperature), yielded ethylene glycol (95%) in just 30 minutes under the same conditions. Similar results were observed with glycol aldehyde, which yielded methanol (83%) and glucoheptose which yielded glucitol (88%) (Example 5). A practical demonstration of the utility of this reaction is provided by the one-step conversion of commercially available 2-deoxyribose (Example 6) into the much less accessible 1-deoxyerythritol (30 min., >90%). This is particularly significant in that the best known synthesis of 1-deoxyerythritol requires seven steps from glucose [Chaby, R., et al., Tetrahedron, 27:3197-3205 (1971)].

Sources & evidence

ORD record
ord-1e8af29a3edd495daca5c673899d5589
Source dataset
uspto-grants-1991_05
Patent number
USH0000918

Reaction notes

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