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Please login or sign up for a free trial to access the full content. Deprotonative Construction of a Carbon–Carbon Single Bond

DOI: 10.1055/sos-SD-134-00125

Yamazaki, T.Science of Synthesis Knowledge Updates, (20172293.

The most straightforward and familiar method in this category starts with the deprotonation of a fluorinated compound at the α-position to an appropriate electron-withdrawing functional group, and then nucleophilic attack of the resultant active species on an appropriate electrophile. For example, the addition of lithium hexamethyldisilazanide to a mixture of fluoro(phenylsulfonyl)methane and a chalcone effects removal of the most acidic proton in fluoro(phenylsulfonyl)methane, and this is followed by its quick nucleophilic attack on the chalcone (Scheme 15).[‌28‌] This process in principle affords a mixture of 1,2- and 1,4-addition products, 35 and 36, respectively, and is sensitive to the solvent system. Thus, an almost equal mixture of 35 and 36 is obtained in tetrahydrofuran, whereas 35 is formed exclusively in a tetrahydrofuran/hexamethylphosphoric triamide mixed medium. The incorporation of an additional phenylsulfonyl moiety into ­fluo­ro(phenylsulfonyl)methane results in fluorobis(phenylsulfonyl)methane, and the resulting anionic species is much softer in nature and yields 1,4-adducts 37 as the sole products. A similar type of transformation with vinylogous imines is also reported.[‌29‌] Moreover, alkylation of fluorobis(phenylsulfonyl)methane can be performed through a Mitsunobu reaction using a mixture of an alcohol, triphenylphosphine, and di­isopropyl azodicarboxylate;[‌30‌] removal of one of the phenylsulfonyl groups from these products is realized by subjecting them to either sodium/mercury amalgam and sodium hydrogen phosphate in methanol[‌28‌] or activated magnesium in methanol.[‌30‌]

Meeeee 88 Meeeeeeee ee Meeeee(eeeeeeeeeeeeee)eeeeeee eee Meeeeeeee(eeeeeeeeeeeeee)eeeeeee eeee α,β-Meeeeeeeeee Meeeeeee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeeeee Meeee (88/88) Meeeeeee Meeee (%) Mee
Me Me MMM 88:88 88 [‌88‌]
Me Me MMM/MMMM (8:8) >88:8 88 [‌88‌]
Me 8-MeM8M8 MMM 88:88 88 [‌88‌]
Me 8-MeM8M8 MMM/MMMM (8:8) >88:8 88 [‌88‌]
8-MeM8M8 Me MMM 88:88 88 [‌88‌]
8-MeM8M8 Me MMM/MMMM (8:8) >88:8 88 [‌88‌]
Me 8-MeMM8M8 MMM 88:88 88 [‌88‌]
Me 8-MeMM8M8 MMM/MMMM (8:8) >88:8 88 [‌88‌]
8-MeMM8M8 Me MMM 88:88 88 [‌88‌]
8-MeMM8M8 Me MMM/MMMM (8:8) >88:8 88 [‌88‌]
8-MeMM8M8 8-MeMM8M8 MMM 88:88 88 [‌88‌]
8-MeMM8M8 8-MeMM8M8 MMM/MMMM (8:8) >88:8 88 [‌88‌]

M8 M8 Meeee (%) Mee
Me Me 88 [‌88‌]
Me 8-MeM8M8 88 [‌88‌]
8-MeM8M8 Me 88 [‌88‌]
Me 8-MeMM8M8 88 [‌88‌]
8-MeMM8M8 Me 88 [‌88‌]
Me Me 88 [‌88‌]
Me 8-MM8M8 88 [‌88‌]

Meeeeeeeee 8-eeeeeeeeeeee-8-eeee 88 ee e eeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeee, eeeeeeee ee eee eeeeeeee ee ee eeeeeee eeeeeeeee, e eeeeeeeee eeeeee ee eee(η8-eeeee)eeeeeeeeeeeeeeeeeee(MM), eee (M)-8-{8-(eeeeeeeeeeeeeeeee)eeeeee}-8-eeee-eeeee-8,8-eeeeeeeeeeeeee [(M)-e-Me-MMMM, 88] eeeee ee eeeeeeeeee ee eee eeeeeeeee M-eeeeeeee eee eeeee eeeeeeee 88 ee eeeeeeee ee eeee eeeeeeeeeeee eeeeeeee ee 88–88% (Meeeee 88).[‌88‌] Mee eeeeeeeeee, eee eeeeeeeeeeeee eee-eeeeeeeeeee eeeeee eeeeee eeeeeee 88 eeee 88% ee, 88% eeeee eeee eeee eeeeeeee ee eee eeee ee 88 (88% ee eee Me8 = Me). Me eee eeeee ee e eeeeeeee eeeee, eeee eeeeeeeeeee ee eeeeeeeeee ee e eeeeeeeeeee ee eee eeeee M/M eeeeeeeeeee ee eee eeeeeee eeeeeee eeee 8-eeeeeeeeeeeeeee.[‌88‌]

Me eee eeeee eeee, eee eeeeeeee ee e eeeeeeeee eeeeee ee eeeeeeeee(MM) eeeeeee eee 8-(eeeeeeeeeeeeeeeeeeeee)-8′,8′-eeeeeeeeeeeeeeeeeeee (MeMeee, 88) eeeeeee eeeeeeeeeeee ee e eee M—M eeee ee eeeeeeeeeee eeeeee 88 eeee e eeeeeee ee eeee eeeeeeee eeeeeee eee eeeeeee eeeeeeeeeeeee eeeeeeee. Meee eeeeee eeeeeeee eeeeee 88 (Me8 = 8-Mee) ee 88% eeeee, eee eeeeeeeeeee ee eee eeeeeeeee eeeeeeee ee eee eee-eeeeeeeeeee eeeeee eeeeeee ee e eeeeeee eeeee ee 88% eee 88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeee eee Meeeeeeee ee α-Meeeee Meeeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

Me8 M8 eee (%) Meeee (%) Mee
Me M 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
8-MeMM8M8 M 88e 88 [‌88‌]
8-MeM8M8 M 88 88 [‌88‌]
8-MeM8M8 M 88 88 [‌88‌]
8-MeM8M8 Me 88 88 [‌88‌]
8-MeM8M8 M 8e 88 [‌88‌]

e Meeeeeeeee ee MMMM.

e Mee ee eee eeeeeeeeee eeeee Meeeee eeeeeeeee.

Me8 Meeee (%) Mee
Me 88 [‌88‌]
8-Mee 88 [‌88‌]
8-MeM8M8 88 [‌88‌]
8-MeM8M8 88 [‌88‌]
8-M8MM8M8 88 [‌88‌]
8-Mee 88 [‌88‌]

M-(eeee-Meeeeeeeeeeeee)-8-eeeeeeeeeeeeeee 88 eee eeee eeeeee eeeeeeeeee eee eee eeeeeeeeeeee ee eee M—M eeeee eeeee eee eeeeeeeee eeeeee ee eeeeeeeee-eeeeeee eeeeeeeee eeee 88, eeeeeee eee eeeeeeeeeee ee eeeeee eeeee eeee ee eeeeeee eeeeeeeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeee.[‌88‌] Meee eeeeeeeeeee eeeeeee ee eeeeeeeee ee eeeeeeeee eeeeeeee ee 88 ee eee eeeeeee eeeeee eeee ee eee eeeeee, eee eeee eeeeeeeeeeee eeeeeeee ee eee eeeeeeee ee eee eeeeeeee eeeeee eeee ee eee eeeeeeeeeeee eeee eeeeee eeeeee. Me e eeeeeeeeeee, eeee eeeeeeee eeeeeee eeeeeeee 88 ee eeeeeeeee eeeeeeee eeeee eee eeeeeeeeeeee eeeeeeeeeee (Meeeee 88). Mee eeeeeeeeee ee eee eeeee eeeeee ee eeeeeeee 88 ee eeeeeeeeeeeee eeeeee ee eeeeeeeeeee ee eee eeeeee ee eee eeeee eeeeeeee eeee ee e eeeeee eeeee, eeeee eeeee ee e eeeeeeeeeee eeeeeeee ee eee eeeeeeeeeeee eeeeee eeeee eeee 88 ee 88% ee eeeeeee 88 (M8 = M8 = M8 = M). Meee eeeeeee ee eeeeeeeeeee ee ee eee eeeeee ee eeeeeeeeeeee ee eeeeeeeeeeeeee eeeeeeee eeeeeee eeee eeee eee eeeeeeee eeeeee eeeee ee eeeeeeeee 88.

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeeee ee 8-Meeeeeeeeeeeeee eee Meeeee Meee-8,8-eeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meee (e) eee (%) Meeee (%) Mee
M M M 8 88 88 [‌88‌]
Me M M 8.8 88 88 [‌88‌]
M Me M 8.8 88 88 [‌88‌]
M Me M 8 88 88 [‌88‌]
MM8 M M 8 88 88 [‌88‌]
Me M M 8 88 88 [‌88‌]
MMe M M 8 88 88 [‌88‌]
Me M Me 8 88 88 [‌88‌]

e Meeeeeeeee ee MMMM.

Mee ee eee eeeeeeee eeeeeee ee eee eeeeeeee eeeeee ee eeeeeeeee eeeeeee eeeeeeeee, ee ee eeeee eeee ee eeeeeeeeee eee eeeeeeeeee ee eee eeeeeeeeeeeee 8-eeeeee eeeeeeeeeee. Mee eeeeeee, eeeeeeeeee eeeeeeeeee ee eee 8-eeeeeeee ee 8-eeeeeeeeeeeeee 88, eeeee eeeee ee eeeeeeeeeeeee eeeee eeeeeeeee, eeeeeeee eeeeeeee ee eeeeee eeeeeeeeeeeee eeeeeeee 88 ee eeeeee eeeeeeeeeeee eeeeee eeee eeeeeeeee eeeeeee eeeeeeee ee eeeeeeeee eeeeeeeeee eeeeeeee eeee 88[‌88‌] ee eee eeeeeeee (Meeeee 88).[‌88‌] Meeeeee eeeeeeeeee eeeeee ee eee eeeeeeeeee eeeeeeeeee–Meeeeee eeeeeeee eeeeeee;[‌88‌] eee eeeeee eeee ee eeeeeeee ee eee eeeee eeeeee eeeeee ee eee eeeee eeee.[‌88‌] Me eee eeeeeeeeeeeeeee eeeee ee eeeeeeee 8-eeeeeeeeeeeeee ee eeeeeeee ee e eeeeeeeeeeeeee eeeee, eee eeeeeeeeeeeeeee eeeee ee eeee eeeeee eeee eee eeeeeeee eeeee ee eee eeeeeeeeee–Meeeeee eeeeeeee, eee ee eeeeeeeeee eeee eee eeeee eee eee eeee eeeee eee eeee, e eeeeeee ee eeeeeeee ee eeeeeeee eeeeeeeee eeee eeeeee eeeeeeeeeeeeeee ee eeeeeeeeeee.

Meeeee 88 Meeeeeeee ee 8-Meeeeeeeeeeeeee ee eee 8-Meeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

M8 Meee (e) eee (%) Meeee (%) Mee
Me 88 88 88 [‌88‌]
MM8MM=MM8 88 88 88 [‌88‌]
Me 88 88 88 [‌88‌]
8-MeeMM8 88 88 88 [‌88‌]
8-MM8M8MM8 88 88 88 [‌88‌]
88 88 88 [‌88‌]

e Meeeeeeeee ee MMMM.

M8 M8 Meee (°M) (Meee 8) Meeee (%) Mee
Me 8-eeeeeeee 88 88 [‌88‌]
Me 8-eeeeeeee 88 88 [‌88‌]
Me 8-MeM8M8 88 88 [‌88‌]
Me Me 88 88e [‌88‌]
Me (MM8)8Me 88 88e [‌88‌]
Me 8-eeeeeeee 88 88 [‌88‌]

e 88 °M ee eee eeeeee eeee.

Meeeeeeeeeee Meeeeeeee

(8M)-8,8-Meeeee-8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-ee-8-eee 88 eee 8,8-Meeeee-8-eeeeee-8-­(eeee­eeeeeeeeee)eeeee-8-eeee 88; Meeeeee Meeeeeeee eee eee Meeeeeee Meeeeeee ee Meeeee(eeeeeeeeeeeeee)eeeeeee ee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeeeeeeeeeeeeeeee eeeeeeee ee e eeeeeeee eeeee eeeeeeeeee eee ee eee eee eeee eeeeeeee.

Meeee e M8 eeeeeeeeee, e Meeeeee eeee eee eeeeeee eeee eee eeeeeeee (888 ee, 8.8 eeee), e eeee ee MeMM8MM8M (88 ee, 8.8 eeee) ee MMM (8.8 eM), eee MMMM (8.8 eM); eee eeeeeee eee eeeeee ee −88 °M, eee e 8.8 M eeee ee MeMMMM ee MMM (8.8 eM, 8.8 eeee) eee eeeee eeeeeeee. Mee eeeeeee eee eeee eeeeeee eeeeeeeeee ee −88 °M eee 88 eee eee eeeeeee eeeeeeee ee eeeeee eee. ee MM8Me. Meeee eee eeeee eeeeee, eeeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 8:8) eeeeeeee eee eeeee eeeeeeeee. 88M MMM (MMMe8, 888 MMe, δ): 88 (M8 = M8 = Me), −888.8 (e, M = 88 Me), −888.8 (e, M = 88 Me); 88 (M8 = M8 = Me), −888.8 (ee, M = 88, 88 Me, eeee), −888.8 (ee, M = 88, 88 Me, eee).

8-Meee-8-eeeeee-8-eeeeeeeeeeee-8-eeee 88; Meeeeee Meeeeeeee eee eee Meeeeeeee ee α-Meeeeeeeeee Meeeeee:[‌88‌]

Me eeee-eeeee Meeeeee eeee eeeeeeeeee e eeeeeeee eeeeeee eee eee eeeeeee eeee Me(MMe)8 (88.8 ee, 8.88 eeee), MeMeee (88; 88.8 ee, 8.88 eeee), eee M8MM8•8M8M (888 ee, 8.8 eeee). Mee Meeeeee eeee eee eeeeee eeee e eeeeee eeeeee eee eeee eeeeeeeee eee eeeeeeeeee eeee eeeee (8 ×). Meeeee (8 eM) eee eeeee eeeeeee eee eeeeee ee eeeeeee, eee eee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 8 eee. Meee, α-eeeeee eeeeee 88 (8.8 eeee) eee ee eeee eeeeeee (8.8 eeee) eeee eeeee. Mee Meeeeee eeee eee eeeeee, eee eee eeeeeee eee eeeeee ee 888 °M eeee eeeeeeee eeeeeeee eee 8 e. Mee eeeeeee eee eeeeee ee ee eee eeeeeeee eeee M8M (88 eM). Mee eeee eee eeeeeeeee eeee Me8M (8 × 88 eM), eee eee eeeeeeee eeeeeee eeeee eee eeeeee eeee eeeee, eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/MeMMe 888:8) ee eeeeee eee eeeee eeeeeeee. Meeeeeeeeeeeee MMM eeee eee 88 (Me8 = 8-Mee): 88M MMM (MMMe8, 888 MMe, δ): −888.8 (e, M = 88.8 Me).

Meeeee 8-eeeeee-8-(eeeeeeeeee-8-ee)eeeeeeeeee (88, M8 = Me; M8 = 8-Meeeeeee); Meeeeee Meeeeeeee:[‌88‌]

Meeee ee eeeeeeeeee ee M8, e 88-eM Meeeeee eeee eee eeeeeee eeee eeeeeeee 8-eeeeeeeeeeeeee (8.8 eeee) eee eeeee MMM (8.8 eM), eee eeee eee eeeeeeee ee eee eeee eeeeeeee ee 88% MeM ee eeeeeee eee (88 ee, 8.8 eeee) ee 8 °M. Meeee eeeeeeee eee 88 eee, 8-eeeeeeeeeeeeee eeeeeee (8.8 eeee) eee eeeee, eee eee eeeeeee eee eeeeeee eeeeeeeeee ee 88 °M eee 8.8 e eeeee eeeeee eeee eeeeeeeeeee ee eee eeeeeee (MMM eeeeeeee). Meee, eee eeeeeee eee eeeeee ee 88 °M eee 88 e. Meeee eeee eeeeeeeeee ee eee eeeeeeeeeeee eeeeeeee eeeeeeeeee (MMM eeeeeeee), eee eeeeeeee eee eeeeeeee ee eeeeee eee. MM8Me eeee (8.8 eM), eee eee eeeeeee eee eeeeeeeee eeee MeMMe (8 × 8 eM). Mee eeeeeeee eeeeeee eee eeeee (Me8MM8). Meeee eeeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeee eeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeeeeee eeeee/e-MeMMe 88:8 ee 88:8) ee eeeeee eee eeeeeee eeeeeee; eeeee: 88%.