Gem-difluorinated homoallyl alcohols, β-hydroxy ketones, and syn- and anti-1, 3-diols via γ,γ-difiuoroallylboronates

Organic Letters

Volumn 10, Issue 6, 2008, Pages 1195-1198

  Ramachandran, P Veeraraghavan ^a   Chatterjee, Anamitra ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL ALCOHOL; BORONIC ACID DERIVATIVE; KETONE; PROPANOL;

ARTICLE; CHEMISTRY; STEREOISOMERISM; X RAY CRYSTALLOGRAPHY;

BORONIC ACIDS; CRYSTALLOGRAPHY, X-RAY; KETONES; PROPANOLS; STEREOISOMERISM;

EID: 45549089899     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol800069z     Document Type: Article

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32. 4). concentrated, and distilled to provide benzyl-2, 2, 2-trifluoroethyl ether as a colorless liquid (32 g, 94%). bp 80 °C/30 Torr.
33. 4), and evaporated. The residue was distilled to yield l-benzyloxy-2.2-difluoroethene as a colorless viscous liquid (5.2 g, 76%). bp. 70 °C/30 Ton',
34. (c) Preparation ofβ-benzyloxy-γ, γ-difluoroa11ylboronate (1): n-BuLi (12.2 mL. 2.5 M solution in hexane, 30.4 mmol) was added, slowly at-78 °C, to a solution of l-benzyloxy-2, 2-difluoroethene (5.2 g, 30.4 mmol) in THF (60 mL) and at that temperature for 20 min. Diisopropyl iodomethylboronate (8.2 g. 30.4 mmol) was added slowly, at -78°C, to the resultant red solution, left stirred for 0.5 h, allowed to warm to rt, and continued to stir for 2 h. The solvents were removed under vacuo, and the residue was triturated with dry pentane (30 mL). The supernatant was filtered through a short bed of celite under inert atmosphere. The residue was washed with pentane (4 x 20 mL), and the combined organics was concentrated and distilled to yield β-benzyloxy-γ, γ-difluoroal1ylboronate (1) as a colorless liquid, bp. 79-82 °C/0.2 Torr.
35. 4), concentrated, and purified by flash silica gel chromotography (hexane:ethyl acelate = 4:1) to yield homoallylic alcohol 5a ( 0.48 g, 82 %) as a colorless viscous liquid.