1-Heptyne → a-[(tetrahydro-2H-pyran-2-yl)oxy]dec-4-yn-2(R)-ol

HRID 2351255

Reaction equation

HRID 2351255 reaction equation
CCCCC/C=C\C[C@@H](O)/C=[CH:11]/[CH:12]=[CH:13]/[CH:14]=[CH:15]\[C@@H:16](O)[CH2:17][CH2:18][CH2:19][C:20]([OH:22])=O.C1[O:27][C@H]1CO.O=C1O[C@H:36]([C@H:38]([CH2:40][OH:41])O)[C:34](O)=[C:32]1O.C#CCCCCC>CCOCC>[O:41]1[CH2:32][CH2:34][CH2:36][CH2:38][CH:40]1[O:22][CH2:20][C@H:19]([OH:27])[CH2:18][C:17]#[C:16][CH2:15][CH2:14][CH2:13][CH2:12][CH3:11]

Participants

6

Reactant 4

HCID 123501-HeptyneHCID 5280492Leukotriene B4HCID 6973630(-)-GlycidolHCID 54670067L-Ascorbic Acid

Product 1

HCID 14464847a-[(tetrahydro-2H-pyran-2-yl)oxy]dec-4-yn-2(R)-ol

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

The starting material for the process of this invention, compound 2, can be prepared as described in Nicolaou, K. C. et al., "A General and Stereocontrolled Total Synthesis of Leukotriene B4 and Analogues," J. Am. Chem. Soc., 106, 3548 (1984) or Hanson, R. M. and Sharpless, K. B., J. Org. Chem., 51 1922 (1986). Briefly, optically active (S)-glycidol THP ether is prepared from ascorbic acid as disclosed in Takano, S., Numata, H., Ogasawara, K., Heterocycles, 19, 237 (1982) and Baldwin, J. J., Raab, A. W., Mensler, K., Arison, B. H., McClure, D. E., J. Org. Chem., 43, 4876 (1978). The ether is reacted (-78°-25° C.) with two equivalents of the anion of 1-heptyne (1.0 equiv. of n-BuLi, 1.0 equiv. of TMEDA and THF, -78° C.) to afford a-[(tetrahydro-2H-pyran-2-yl)oxy]dec-4-yn-2(R)-ol which is then silylated (t-BuPh2SiCl, imidazole, DMF) to, compound 2.

Sources & evidence

ORD record
ord-491ea872368f4a6580fbc8c0e583bfc3
Source dataset
uspto-grants-1989_10
Patent number
US04873024

Linked notes

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