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24.2.3.1.5 Method 5: Wittig-Type Reactions

DOI: 10.1055/sos-SD-024-00188

Khlebnikov, A. F.; Kostikov, R. R.Science of Synthesis, (200624180.

It is well-known that carbenoids react with phosphines to form phosphorus ylides. Thus, treatment of chlorofluoro(phenylsulfanyl)methane with butyllithium in the presence of triphenylphosphine at 78°C gives a yellow ylide, which is treated with 3-phenylpropanal to give 1-fluoro-1-(phenylsulfanyl)-4-phenylbut-1-ene [42, R1=(CH2)2Ph] in 63% yield with low Z selectivity (E/Z 2:3); the use of methyllithium in the presence of lithium bromide as a base increases the yield of 42 [R1=(CH2)2Ph] to 75% but decreases the selectivity (E/Z 1:1). A similar reaction with biphenyl-4-carbaldehyde gives 2-(biphenyl-4-yl)-1-fluoro-1-(phenylsulfanyl)ethene (42, R1=4-PhC6H4) in 80% yield with an E/Z ratio of 1:1 (Scheme 32).[‌53‌]

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MeeeeeMeeeeeeeeMeeeee eeeeeeeee ee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee eeee eeeeeeee eeeeeeeee eeeeeee eeeeeeee ee eeee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88 ee eeee ee eeee eeeeee (Meeeee 88).[‌88‌]

Meeeee 88 8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (M/M) Meeee (%) Mee
M Me M eeee 88 [‌88‌]
M M 88 [‌88‌]
M 8-MeMM8M8 88:8 88 [‌88‌]
Me MM8Me 88:88 88 [‌88‌]
Me Me 88:8 88 [‌88‌]
M MM=MMMe M eeee 88 [‌88‌]
M Me 88:88 88 [‌88‌]
M 8-M8MM8M8 88:8 88 [‌88‌]
M MM8Me 88:88 88 [‌88‌]
Me Me 88 [‌88‌]
(MM8)8 88 [‌88‌]
Me 8,8,8-eeeeeeeeeeeeeeeee-8-eeeeeeeee 88:88 88 [‌88‌]

Me eeeeeeeee eeeeeeeee ee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88 eeee eee eeeeeeeee ee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee, eeeeeeeee ee eeee eeee eeeeee(eeeeeeeeeeeeee)eeeeeee eee eeeeeee eeeeeeeeeeeeeeee ee eeeeeee eeeeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌88‌] (M)-8-[Meeeee(eeeeeeeeeeeeee)eeeeeeeee]-8-eeeeeeeeeeeeeeeee [88, M8,M8=(MM8)8MMMe] ee eeeeeeee ee 88% eeeee eeeeeeeee ee eeee eeeeeeee.[‌88‌]

Meeeee 88 8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee[‌88‌,‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (M/M) Meeee (%) Mee
Me 8,8-(MeM)8M8M8 8:8 88 [‌88‌]
Me Me 88 [‌88‌]
M 8-MeM8M8 8.8:8 88 [‌88‌]
Me Me 8.8:8 88 [‌88‌]
Me Me 88 [‌88‌]
M (MM8)88Me 8.8:8 88 [‌88‌]
(MM8)8MMMe M eeee 8888 [‌88‌]

Meeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee, eeeeeeee ee eeeeeeeeeeee ee eeeeeee (eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee eeee M-eeeeeeeeeeeeeeeee, ee eeeeeeeeeeeee eeee eeeeeeeeeeee eeeeee eeee eeeeeeeeeeee ee eeeeeeeeeeeee ee eeeee eeeeeeeee eee eeeeeeeeeeeee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88 (Meeeee 88).[‌88‌] Meeeeeeee ee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee eeee eeeeeeee eeeeeeee ee eeeeee eeee ee eeee 8-eeeeeeeeeeeeeeeeeee eeee ee eeeeeeeeee eeeee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee eeeee, eeeee eeeeeeeeeeeee eeee eeeeee eeeeeee ee eeeeeeeeeeeeeee, eeeeee eeee eeeeeeeee ee eeee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88 ee 8888% eeeee (Meeeee 88).[‌88‌]

Meeeee 88 8-Meeeee-8-(eeeeeeeeeeeeee)- eee 8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee[‌88‌]

8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88 eee eeeeeeeeeeee eeeeeeee ee eeee eeeeee eeee eeeeee(eeeeeeeeeeeeee)eeeeeee eeeee e eee-eee MeeeeeMeeeeeeeeMeeeee eeeeeeee eee eeeeeee eeeeeeeeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee (Meeeee 88).[‌88‌]

Meeeee 88 8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee ee Mee-Mee MeeeeeMeeeeeeeeMeeeee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meee (e) Meeee (M/M) Meeee (%) Mee
Me M 8 88:8 88 [‌88‌]
8-MeM8M8 M 8 88:8 8888 [‌88‌]
8-MeMM8M8 M 8 88:8 88 [‌88‌]
8-eeeee M 8 88:8 88 [‌88‌]
(MM8)8Me M 8 88:88 88 [‌88‌]
Me M 8 88:88 88 [‌88‌]
Me Me 88 88 [‌88‌]
(MM8)8 88 88 [‌88‌]

Meeeeeeee ee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee eeeeee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee ee e eeeeeee ee eeeeeeeeeeeee. Mee MeeeeeMeeeeeeeeMeeeee eeeeeeee ee eeee eeeeeeeeeeee eeee eeeeeeeee eeeeeeee 8-eeeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88 (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeee ee 8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (M/M) Meeee (%) Mee
Me 8:8 88 [‌88‌]
Me 8:8 88 [‌88‌]
eMe 8:8.8 88 [‌88‌]
Me 8:8 88 [‌88‌]

8-Meeeee-8-(eeeeeeeeeeeee)eee-8-eeee 88 eee eeeeeeee ee Meeeee-eeee eeeeeeeee ee e eee-eee eeeeeeeee (Meeeee 88). Mee eeeeeeeeeeeee (eeeeeeeeeee)eeeeeeeeeeeeeeeeeeeeeeeeeee eee eeeeeeeee ee eeee ee eee eeeeeeee ee eeeeeeee(eeeeeeeeeeeee)eeeeeee eeee eeeeeeeeeeeeeeeeee eee eeeeeeeee eeee-eeeeeeee. Mee eeeeeeeeeeee eeeee eeee eeeeeeeee ee eeeee 8-eeeeee-8-(eeeeeeeeeeeee)eee-8-eeee 88 ee e M/M eeeeeee eeee eee eeeeeeeeeeeeeeeee (8.8:8 ee 8:8).[‌88‌]

Meeeee 88 8-Meeeee-8-(eeeeeeeeeeeee)eee-8-eeee[‌88‌]

Meeeeeeeeee 88

M8 Meee (e) Meeee (%) Mee
Me 8.8 88 [‌88‌]
8-Mee 8.8 88 [‌88‌]
8-MeM8M8 8.8 88 [‌88‌]
8-M8MM8M8 8.8 88 [‌88‌]
8-eeeee 8.8 88 [‌88‌]

Mee eeeeeee eeeeeeeeeee eeeeeeeee eeee eeeeeee (eeeeeeeeeeeee)eeeeeeeeeeeeeeeee eeee eeeeeeeeeeee ee 88°M eeeee eeee eeeeee eeeeeeeeeeeee ee eeee eeeeeee eeeeee(eeeeeeeeeeeee)eeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeeeeeeeeee (Meeeee 88). Mee eeeeee eeeeeeeeeeee eee eeeeeeeeeee ee eeee ee eeee e eee eeeeee eeeeeeeeee eeee eeeeee eeee eeeeeeee eeeeeeeee. Mee eeeee eeee eeeee ee eee eee eee eeee ee 8-eeeeee-8-(eeeeeeeeeeeee)eee-8-eeee 88.[‌88‌]

Meeeee 88 8-Meeeee-8-(eeeeeeeeeeeee)eee-8-eeee eeee Meeeeee (Meeeeeeeeeeee)eeeeeeeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeee-8-(eeeeeeeeeeeeee)eeeeee (88, M8=M8=M); Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeeeeee ee MeM (8eeee) ee MMM eee eeeee ee 88°M e eeee ee eeeeeee eeeeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee (8eeee ee MMM), eee eee eeeeeee eee eeeeeee eee 8e. Me eeee eeee eee eeeee eeeeeeeeeeeeeeee (88eeee), eee eee eeeeeeee eee eeee ee 8°M eee 88e. Mee eeeee eeeeee eee eeeeee eeeeeeeeeeeeee eeee eee eeeeeee; eeeee: 88%.

8-Meeeee-8-(eeeeeeeeeeeeee)eee-8-eeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eeeeee(eeeeeeeeeeeeee)eeeeeee (8eeee) ee eeeee MMM (8eM) eee eeeee eeeeeeee 8.8M MeMe ee eeeeee (8.88eM, 8eeee) ee 88°M. Meeee eeeeeeee eee 8e ee eeee eeeeeeeeeee, e eeee ee eeeeeee eeeeeeeeeeeeeee (8eeee) ee MMM (8eM) eee eeeee eeeeeeee, eee eee eeeeeee eee eeeeeee ee 88°M eee 88eee. Me eee eeeeeee eee eeeee ee 88°M e eeee ee eee eeeeeeee eeeeeeee (8eeee) ee MMM (8eM). Mee eeeeeeeee eeee eee eeeeee ee ee eeeeee 8e eee eeeeeee eee ee eeeeeeeeee eeee (Meeeee 88). Mee eeeee eeeeee eeee eee eeeee eeeeeeee 88 eeee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).

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

Me e eeee ee eeeeeeee(eeeeeeeeeeeee)eeeeeee (8.88e, 8.8eeee) eee Me8M (8.88e, 8.8eeee) ee eeeee MMM (8eM) eeeee M8, eee eeeee e-MeMM (8.88e, 8.8eeee) ee eeeeeeee. Mee eeeeeee eeeeee eeeeeee, eee eeeee 8eee MeMMM (8.8eeee) eee eeeee. Mee eeeeeee eee eeeeeee ee ee eee 88eee, eee eeeeeeee eee eeeeeeee eeee M8M (88eM), eee eee eeeeeee eee eeeeeeeee eeee MeMMe (8×88eM). Mee eeeeeeee eeee eeeee (MeMM8) eee eee eeeeeee eee eeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee); eeeee: 888ee (88%).

8-Meeeee-8-(eeeeeeeeeeeee)eee-8-eeee 88; Meeeeee Meeeeeeee:[‌88‌]

Meeee eeeee, 8.8M MeMe ee eeeeee (8.88eM, 8.88eeee) eee eeeee eeeeeeee ee 88°M ee eeeeeee (eeeeeeeeeeeee)eeeeeeeeeeeeeeeee (8e, 8.8eeee) ee MMM (88eM). Mee eeeeeee eee eeeeeee ee 88°M eee 8e, MMe8 (8.8e, 8.88eeee) (MMMMMMM: eeeee) ee MMM (88eM) eee eeeee eee eeeeeeee eee eeeeeeeee eee 88eee. Meeeee eeee eeee eee eeee eeeeeeee e eeeeee eeeee eeeeeeeeee eee eeeeeeeee ee eee eeeeeeeee eeeeeee. Mee eeeeeeee eeeeeeee (8.8eeee) ee MMM (88eM) eee eeeee. Meeeeeee eee eeeeeeeee ee 88°M eee 8e, eee ee ee eee 8e. Mee eeeeeee eee eeee eeeeeeeeee ee eeeeeeee ee M8M (88eM). Mee eeeeeee eee eeeeeeeee eeee Me8M (8×88eM), eee eeeeeee eeeee eee eeeee (MeMM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee).

References


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