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Volumn 125, Issue 10, 2003, Pages 2958-2963

Development of a highly α-regioselective metal-mediated allylation reaction in aqueous media: New mechanistic proposal for the origin of α-homoallylic alcohols

Author keywords

[No Author keywords available]

Indexed keywords

ALDEHYDES; ALLYL RESINS; CATALYSIS; CHEMICAL BONDS; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SOLUTIONS; STEREOCHEMISTRY;

EID: 0037433608     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja029276s     Document Type: Article
Times cited : (176)

References (76)
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    • A small amount of THF (0.3 equiv) must be added to suppress the formation of side product to afford 78% yield with an α to γ ratio of 70/30. This is because the corresponding α-adduct undergoes an oxonium-ene cyclization with aldehyde immediately once the α-adduct was synthesized. For reference, see: Loh, T. P.; Hu, Q. Y.; Tan, K. T.; Cheng, H. S. Org. Lett. 2001, 3, 2669.
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    • We also tried to add 6 equiv of water to the reaction; yet, a lower yield was obtained. For example, reaction of hexanal aldehyde with cinnamyl bromide in 6 equiv of water for 24 h afforded only 22% yield with no change in regioselectivity.
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    • The single-crystal X-ray diffraction analysis data have been published, see: ref 10b and Loh, T. P.; Hu, Q. Y.; Ma, L. T. Org. Lett. 2002, 4, 2389.
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    • We found that InBr can catalyze the rearrangement of γ-adducts to their corresponding α-adducts too.
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    • 3 to the γ-adduct in various solvents, including 6 equiv of water, DMF, and THF. Results revealed that after 72 h at room temperature, only the mixture in 6 equiv of water showed signs of rearrangement (γ: α ≈ 78:22), while those in DMF and THF showed no progress. In fact, when 12 equiv of water was used, no rearrangement was observed as well.


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