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Please login to access the full content or check if you have access via34.7.1.1.1 Method 1: Deoxofluorination of Allylic Alcohols with N,N-Diethylaminosulfur Trifluoride
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Roig, R.; Percy, J. M., Science of Synthesis, (2005) 34, 319.
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]
Meeeee 8 Meeeeeeeeeeeeeeee ee Meeeeee Meeeeeee eeee M,M-Meeeeeeeeeeeeeeeee Meeeeeeeeee[8]
Mee eeeeeeeeeee eeeeeee eeeeeeeeeeee eeee eee eeeeeee eeeeeeeeeeeee ee eeeeeeee ee eeeeeeeee eeeeeeeee eeeeeeeee.[8] Me eeeeeeee ee eee eeeee eeeeee, eee eeeeee eeeeeeeeeee eee e eeeeee eeeeee ee eee eeeeeeeeeeeeeeee. Mee eeeeeee, eee eeeeeeee ee 8-eeeeeeeee-8-ee-8-ee (8, M8 = Me; M8 = Me) eeee M,M-eeeeeeeeeeeeeeeeee eeeeeeeeeee eeeeee eeee eeeeeeee eeeeeeeeeeeee eeeeee eee eeeeeeeeee eeeeee 8 (M8 = Me; M8 = Me) eeeeeeeeeee (Meeee 8, eeeee 8). Mee eeee eeeeeeeeee ee eeeeeeee eeeeeeee eeee 8-eeeeeeeee-8-ee-8-ee (8, M8 = Me; M8 = Me). Me eeee eeee, eee eeeeeeeeeeee eeeee eeeeeee ee eee eeee eeeeeeeeee, eee eeeeeeee eee eeee eeeeee eeeeeeeeee. Meeeeee, ee eeee ee eeeee eeee eeeee eee eeee eeeeeeeeee, eee eeeeeeee ee 8-eeeeeeeeee-8-ee-8-ee (8, M8 = Me; M8 = M) eeee M,M-eeeeeeeeeeeeeeeeee eeeeeeeeeee eeeeee e 88:88 eeeeeee ee 8 (M8 = Me; M8 = M) eee 8 (M8 = Me; M8 = M), ee eeeeeeeeee ee MMM eeeeeeee ee eee eeeee eeeeeee. Meeeeee 8 (M8 = Me; M8 = M) eeeeeee ee ee eeee eeeeeeeee ee eeeeee eee, eeee 8 (M8 = Me; M8 = M) eeeee eee eeee eeeeeeee eeeeeeeeeee. Meee eeeeee ee eeeeeeeee eeeee ee eeeeeeeee e eeeeeeeeee eee eee eeeeeeeee ee eee eeeeeeeee eeeeeeee eeeeee eee eeeeeee, ee eeeee ee eee eeee eeee eeeeeeeeeee ee eee eeee eeeee eeee eee eeeeee eeee eeeeee eeee ee 8 (M8 = Me; M8 = M).
Mee eeeeeeeeeeee ee eeeeeeee eeeeeeee-eeeeeeeeeee eeeeeeeeeeee eeeeeee eee eeeeeeeeeee ee eeeeeeeeeeee eee eeeeeeeee ee eee eeeeeeeeee eeeeee, eeeee eeeeeeee e eeeeee eeeeee ee MM8 eeeeeeeee, eeeeeeeee eee eeeeeeeeeeeeeeee eee eeeeeeeeee eee eeeeeeeeeeeee. Me ee eeeeeee ee eeee eeeeeeee, eeeeeee 8–8 ee Meeee 8 eeee eee eeeeeeeee ee eeeeeeee 8 eeeeeeeeeee, eeeeeee eeeeeeeeeeeee.[8]
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 88–88°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
[1] | Meée, M. M.; Meeeeeeee, M. M. M.; Meeeeeee, M. M.; Meée, M. M.; Meeeeeeee, M.-M.; Meeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[2] | Meeeeee, M. M.; Meeeeee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[3] | Meeeeeee, M.; Meée, M.; Meée, M., M. Mee. Meee., (8888) 88, 8888. |
[4] | Meée, M.; Meeeeeee, M.; Meée, M.; Meeeee, M.; Meeeeeeeee, M.; Meeeeeee, M.-M.; Meeeeeeeee, M.; Meeee, M. M.; Meee, M. M., M. Mee. Meee., (8888) 88, 8888. |
[5] | Me Meeeee, M.; Mee Meeeeeeee, M.; Meeeeee, M.; Meeeeee, M.; Meeeee, M.; Mee Meeeeeeeee, M.; Me Meeeeeeeee, M.; Meeeeee, M.; Meeeeeeee, M., Meeeee. Mee. Meee. Meee., (8888) 8, 8888. |
[6] | Meeeeee, M.; Meée, M.; Meeeeeee, M.; Meée, M., M. Meeeeeee Meee., (8888) 88, 88. |
[7] | Meeeeeeee, M. M., M. Mee. Meee., (8888) 88, 888. |
[8] | Meeeeeee, M., Mee. Meeee. (M. M.), (8888) 88, 888. |
[9] | Meeeeeeeee, M. M.; Me, M.-M., Meeeeeeeeee Meee., (8888) 88, 8888. |
[10] | Meeeee, M., Mee. M. Meee., (8888) 88, 8888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) M 88e, 888.
- 8.Meeeee-Meee, (8888) M 88e, 888.