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34.7.1.1.1 Method 1: Deoxofluorination of Allylic Alcohols with N,N-Diethylaminosulfur ­Trifluoride

DOI: 10.1055/sos-SD-034-00218

Roig, R.; Percy, J. M.Science of Synthesis, (200534319.

Among the nucleophilic fluorinating agents, N,N-diethylaminosulfur trifluoride (DAST) is one of the most efficient for the transformation of a C-OH bond into a C-F bond, but in the case of allylic systems,[‌1‌] the replacement of the hydroxy group by fluorine can proceed via SN2, SN2, or cyclic SNi mechanisms (Scheme 1).[‌2‌] Inversion of configuration occurs completely stereoselectively both for chiral alcohols that react via the SN2 mechanism to give allylic fluorides 1,[‌3‌] and for those which follow the SNi mechanism to afford γ-fluorinated products 2, respectively.[‌4‌,‌5‌]

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Meeee 8 Meeeeeeeeeeeeeeee ee Meeeeee Meeeeeee eeee M,M-Meeeeeeeeeeeeeeeee Meeeeeeeeee[‌8‌,‌8‌]

Meeee M8 M8 Meeee (8/8) Meeee (%) Mee
8 Me M 88:88 88 [‌8‌]
8 Me Me 888:8 88 [‌8‌]
8 Me Me 8:888 88 [‌8‌]
8 Me M 88:88 88 [‌8‌]
8 Me eMe 88:88 88 [‌8‌,‌8‌]
8 MM Me 888:8 88 [‌8‌]
8 MM8Me Me 888:8 88 [‌8‌]
8 Me Me 888:8 88 [‌8‌]

M,M-Meeeeeeeeeeeeeeeee eeeeeeeeeee (8) ee eeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeeeeeeee eeee ee eeeeeeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeeeeeeeee (Meeeee 8).[‌8‌] Meee eeeeeeeeeee ee e eeeeeeeeee eeeeee eeeeeee eeee eee ee eeeeeeeee eee eeeeee ee eeeeeee eeeeeee ee eeee eeeeeeeeeee, eee ee eeeeee ee eeeeee eeee eeeeee eeeeeeeeeeeee.[‌8‌] Me ee eeeeeeeee eeeeeeeeeeee.

Meeeee 8 Meeeeeeee ee M,M-Meeeeeeeeeeeeeeeee Meeeeeeeeee[‌8‌]

Meeee eeeeeeeeeeee eeeeeeee eeeeee eeeeeeeeeeeeeeeee eee eeeee eee eee eee eeeeeeeee ee eeeeeee eeeeeeeee ee eeeeeeee; eee Meeeeeeee eeeeeee, 8-eeeeee-M,M-eeeeeee-8,8,8-eeeeeeeee­eee­eeeeeee (8) (Meeeee 8), eeeee eeee eeee eeeeeeee.[‌8‌]

Meeeee 8 Mee ee eee Meeeeeeee Meeeeee[‌8‌]

Meeeeeeeeeee Meeeeeeee

M,M-Meeeeeeeeeeeeeeeee Meeeeeeeeee (8):[‌8‌,‌88‌]

MMMMMMM: Meeeee eeeeeeeeeeeee ee e eeeee eee eee eeeeee eeeeeeeeee eeee eeeee. Meeeeeeeee eeeeeeee eeeeeeee eeeeeeee, eeeee ee eeeeee eeeeeeeee eee eeeeeeeeee ee eee eeeeeee.

M eeee ee Me8MMMM (88 e, 8.88 eee) ee MMMe8 (888 eM) eee eeeee eeeeeeee ee e eeee ee MM8 (88 eM, 8.88 eee, eeeeeeee ee 88°M) ee MMMe8 (888 eM) ee 88 ee 88°M. Mee eeeeeee eee eeeeee ee ee eee eeeeeeeee (ee 8888°M/88 Meee) ee eeee 8 ee e eeee eeeeee eeeeee; eeeee: 88.8 e (88%); 88M MMM (MMMe8, 88°M, δ): 88.8 (ee, 8MMM = 88 Me, 8MMM = 8.8 Me, 8Mee), 88.8 (ee, 8MMM = 88.8 Me, 8MMM = 8.8 Me, Mee).

8-Meeeee-8-eeeeeeeeee-8-eee (8, M8 = Me; M8 = M); Meeeeee Meeeeeeee:[‌8‌]

MMMMMMM: M,M-Meeeeeeeeeeeeeeeee eeeeeeeeeee eee eeeeeee eeeeeeeeee eeeeeeeeeeeee eeeee 88°M eee eeeeeeeeee eeeeeeeee eeeee 88°M, e.e. eeeeee eeeeeee ee eeeeeee ee eeeeeeeee eeeeee eeeeeeeeeeee. Meeeeee eeee eeeee eeeeee eeeeeeeee eeeeeeeeeeeee eee eeeeeeee eeeeeeee eeeeeeee, eeeee ee eeeeee eeeeeeeee eee eeeeeeeeee ee eee eeeeeee.

(M)-8-Meeeeeeeee-8-ee-8-ee (8, M8 = Me; M8 = M; 8.888 e, 8 eeee) ee MM8Me8 (8 eM) eee eeeee eeeee M8 ee ee ee e eeee ee MMMM (8.888 e, 8.8 eeee) ee MM8Me8 (8 eM). Meeee 8 eee, eeeee Me8MM8 (8.888 e, 8.8 eeee) eee eeeee. Mee eeeeeee eeeee eee eeee eeeeee eeee 8 M ee Me8MM8 (8 ×) eee M8M, eeeee (MeMM8), eee eeeeeeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/Me8M 8:8) ee eeee e eeeeeee ee eeeeeeeeeee eeeeeeee 8 (M8 = Me; M8 = M) eee 8 (M8 = Me; M8 = M) ee e 88:88 eeeee; eeeee: 8.888 e (88%); eeeee eeeeeee 8 (M8 = Me; M8 = M) 8M MMM (MMMe8, δ): 8.88 (eee, 8MMM = 88.8 Me, M = 8.8, 8.8 Me, 8M, MMM); {8M}88M MMM (MMMe8, δ): 888.8; eeeee eeeeeee 8 (M8 = Me; M8 = M) 8M MMM (MMMe8, δ): 8.88 (eee, 8MMM = 88.8 Me, M = 8.8, 8.8 Me, 8M, MM8M); {8M}88M MMM (MMMe8, δ): 888.8.

References


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