1,3-Transposition of primary allylic alcohols: Synthesis of optically active secondary and tertiary allylic alcohols

Tetrahedron Letters

Volumn 38, Issue 26, 1997, Pages 4675-4678

  Dorta, Rosa L ^b   Rodríguez, María S ^b   Salazar, José A ^a   Suárez, Ernesto ^a  

^a INSTITUTO DE PRODUCTOS NATURALES Y AGROBIOLOGÍA   (Spain)

^b UNIVERSIDAD DE LA LAGUNA   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALLYL ALCOHOL;

ARTICLE; CHEMICAL REACTION; DRUG SYNTHESIS; ENANTIOMER; EPOXIDATION; REACTION ANALYSIS;

EID: 0342618462     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)00964-7     Document Type: Article

References (20)

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14. +, 1%).
15. Interestingly, this solvent mixture allows the transformation of primary and secondary alcohols into their corresponding iodides at room temperature and with short reaction times. For example, dihydrocholesterol gives the corresponding 3α-iodide derivative in quantitative yield after 3 h at room temperature. The above compares advantageously with the related reported transformation using toluene alone, for which high temperatures (120 °C for secondary alcohols) and longer reaction times are required: Garegg, P. J.; Samuelsson, B. J. Chem. Soc., Perkin Trans. 1 1980, 2866.
16. 3P(OH)I under the reaction conditions (see mechanism): Sonnet, P. E. Synthesis 1980, 828.
17. Bonini, C.; Federici, C.; Rossi, L.; Righi, G. J. Org. Chem. 1995, 60, 4803.
18. +, 1%).
19. 3PO (2 mmol), HI (57%, 1 mmol), benzene/1,2-dichloroethane 7/3 (10 ml), 0 °C, 5 min.
20. Iodohydrins are quickly formed ( 15 to 30 min at 70 °C) and decompose over longer reaction times.