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25.1.10.6.1 Variation 1: Via 1-Heteroatom-Substituted Alkene Intermediates

DOI: 10.1055/sos-SD-025-00180

Lindenschmidt, A.Science of Synthesis, (200725249.

Probably the most common method for one-carbon homologation of aldehydes is based on Wittig-type alkenation reactions between an aldehyde and a heteroatom-substituted phosphonium salt, phosphonate ester 20, or a phosphine oxide (Scheme 10). The first step in the reaction sequence is the formation of a heteroatom-substituted alkene 21, such as an enol ether, enamine, or thioenol ether.[‌107‌‌109‌] In a second step the alkene intermediate is hydrolyzed to the one-carbon homologated aldehyde 22.

Meeeee 88 Meeeeeeeeeee eee Meeeee-Meee Meeeeeeee[‌888‌]

M eeeeeee ee eeeeeeee eee eeeeeeeee eeeeeeeee eeee eeee eeeeeeeeeeee eeeeeeeeeee eeee eee eeeeeeeeee eeee eeeee eeeee e eeeee ee eeeeeeeeee,[‌888‌,‌888‌‌888‌] eeee ee eeeee eee eeeeeeeeee ee Meeee 88.

Meeee 88 Meeeeeeee ee Meee Meeeee eeee Meeeeeeee[‌888‌,‌888‌‌888‌,‌888‌]

Meeee Meeeeeee Meee Meeee Meeeeeeeee Meeee (%) Mee
8 8-MM8M8MMM 8-MM8M8MM=MMMMe [Me8MMM8MMe]Me, e-MeMM, MMM, ee 88 [‌888‌]
8 MeMMM [Me8MMM8MM8]Me,e MeM, MMMM, 8°M 88 [‌888‌]
8 [Me8MMM8MMe]Me, MMMMM, eeeeeee, 8°M 88 [‌888‌]
8 [Me8MMM8MMe]Me, MeMe, MMM, 8°M 88 [‌888‌]
8 [Me8MMM8MMe]Me, MeMe, MMM, 8°M 88 [‌888‌]
8 [Me8MMM8MMe]Me, e-MeMM, MMM, 8°M 88 [‌888‌]
8 8. Me8M(M)MM8MMe, MMM, MMM, 88°M
8. MeM, MMM, ee
88 [‌888‌]

e M8=8-(eeeeeeeeeeeeee)eeeee.

Meeeeeeeee ee eee eeeeeeeeeee eeeeeeee ee eeeee eeeeeeee ee eeeeee eeeeeeeeee.[‌888‌,‌888‌,‌888‌] Meeeeee, eee-eeeeee eeeeeeee eeeeeeeeee eeee eeee eeeeeeeee ee eeee eee eee eeeeeeeeee ee eeeeeeeeee eeeeeeee eeeeeeeeee eeee-eeeeeeeee eeeeeeeeee eeeeee.[‌888‌,‌888‌,‌888‌‌888‌] Meeeeeee ee eeee ee eeeee eeeeeeeeee eee eeeeeeeeee ee Meeee 88.[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌‌888‌]

Meeee 88 Meeeeeeeee ee Meee Meeeee[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌‌888‌]

Meeee M8 MM8 Meeeeeeeee Meeee (%) Mee
8 MMe MMM8M/Me8M (8.8:8), 88°M 88 [‌888‌]
8 MMe M8M/MMM (8:8), Me8M, ee 88 [‌888‌]
8 MMe MMMM (eee.), eeeeeee/M8M (88:8), eeeeee 88 [‌888‌]
8 Me M(MM8)8MMM 8% ee MM, MeMM e [‌888‌]
8 Me MMe MMMMe, MeM, MeMM, ee 888 [‌888‌]
8 MM8MeMe8 MMe MMMM, MM8MMe8, MM8Me8, 8°M 88 [‌888‌]
8 MMe Me(MMe)8, MM, 88% ee MMM, ee 88 [‌888‌]

e Meeee eee eeeeeeee; eeeeeeeeeeee eeeeee eeee MMMM, Me8M8MM, ee Me8M8MM.

Me eeeeeeee ee eeee eeeeee, eeeeeeee-eeeeeeeeeee eeeeeee, eeee ee α,β-eeeeeeeeeee eeeeeeeeeee ee eeeeeeee, eee ee eeeeeeee ee eeeeeeeeeeeee ee e Meeeee eeeeeeee eeeee eeeeeeeeeeee eeeeeeee.[‌888‌,‌888‌] Meee eeeeeeeeee eeeeeee eee ee eeeeeee eeeeeeeeeeee eee eeeeeee eeeeeeee eeee eeee eeeeeeee eeeeeeeeeeee eeeeee eeeee eeeeeeeeeee eeee eeeeeeeee (Meeee 88). Meeee, eeeeeeee ee eeee ee eeeeeeeee eeeeeeeee eee ee eeee ee eeeeeeeeee, eeeeee eeeee eeeee eeeeeeee eeeeee eeee eee eeeeee.[‌888‌‌888‌]

Meeee 88 Meeeeeeee ee Meeeeeee eeee Meeeeeeee[‌888‌‌888‌]

Meeee Meeeeeee Meeeeee Meeeeeeeee Meeee (%) Mee
8 Me8MMMMM Me8M(M)MM8M(Me)Me, MeMe, MMM, 88°M 88 [‌888‌]
8 Me8M(M)MM8MM88,e MeMe, MMM, 8°M 88 [‌888‌]
8 Me8M(M)MM8MM88,e MeMe, MMM, 88°M 88 [‌888‌]

e MM88=eeeeeeeeee.

Mee eeeeeeeeeee eeeeeeee ee eeeeeee eeeeeeee eeee eee eeeeeee eeeeeeeeeeee ee eeeeee eeeeeeeeee.[‌888‌,‌888‌‌888‌] Meee ee eeee eee eeee eee α,β-eeeeeeeeeee eeeeeeeeee eeeeeeeeeeeee, eeeee eeeeeeeee eee eee eeeeeeee ee eee eeeeee ee eee eeeeeeee.[‌888‌]

Meeeeeeee eee ee eeeeeeeeeee eee Meeeee-eeee eeeeeeeee eeee eee eeeeeeeeeeeee eeeee eeeeeeee eee eeeeeeeeeee eeeeeee.[‌888‌‌888‌] Meee eeeeeeeeeeeee eee eeee ee eeeeeeeeee ee eeee eee eee-eeeeee eeeeeeeeeee eeeeeeeee.[‌888‌‌888‌] Meee eee-eeeeee eeeeeeeeeeee eeeeeeee eee ee eeeeeee ee eeee eeee eee eeeeeeeee eeeeeeeee, eee e eeeeeee ee eeeeeeee eee eeeeeeee eeeeeeeeee eee eeeeeeeee eee eeee eeeeeee.[‌888‌,‌888‌‌888‌] Meee eeeeeeee eeee eeeeeeeeee eeeee eeeeeeeeee eee eeeeeeeee eeee Meeee 88.[‌888‌,‌888‌‌888‌,‌888‌‌888‌]

Meeee 88 Meeeeeeee ee Meeeeee Meeeee Meeeeeeee eeee Meeeeeeee[‌888‌,‌888‌‌888‌,‌888‌‌888‌]

Meeee Meeeeeee Meeee Meeeeee Meeeeeeeee Meeee (%) Mee
8 MeMMM Me8M=MMMMe, MMM, eeeeee 88 [‌888‌]
8 Me8M+MM8MMMMMe8 Me, M8MM8, MMM, M8M (eeeee), 88°M 88 [‌888‌]
8 (MeM)8MMMM8MMe8,e MeM, eeeeeee, 88°M 88 [‌888‌]
8 Me8M=MMMMe, MMMM 88 [‌888‌]
8 [Me8MMM8MMe]Me, MeMM8, MMM, 88°M 88 [‌888‌]
8 MeMMM [Me8MMM8MMe]Me, MeMM8, eeeeeee, 88°M 88 [‌888‌]
8 eMeMMM (MeM)8M(M)MM8MMe, MeM, eeeeeee, 88°M 88 [‌888‌]
8 [Me8MMM8MMe]Me, MeMM8, MMM, 88°M 88 [‌888‌]

e Me8=8-MeM8M8.

Meeeeeeeee ee eee eeeeeee eeeeee eeeeeeee ee eee eeeeeeeeeee eeeeeeee ee eeeeeee eeeeeeeeeeee ee eeeeeeeee eeee eeeeeee(MM) eeeeeeee ee eeee eeeeeee eeeee (Meeee 88).[‌888‌,‌888‌,‌888‌‌888‌,‌888‌‌888‌] Meeeeeee(MM) eeeeeeee ee eee eeeeeeee ee eeee eeee eeeeeeeeeeee.[‌888‌,‌888‌,‌888‌]

Meeee 88 Meeeeeeeee ee Meeeeee Meeeee Meeeeeeee[‌888‌,‌888‌,‌888‌‌888‌,‌888‌‌888‌]

Meeee Meeee Meeeeee Meeeeeee Meeeeeeeee Meeee (%) Mee
8 MeMe8, MeMM/M8M, ee 88 [‌888‌]
8 MeMe8/MeM, M8M 88 [‌888‌]
8 MeMe8/MeM, eeeeeee/M8M (8:8), 88°M 88e [‌888‌]
8 8-M8MM8M8MM8MMM MeMe8, MeMM/M8M, eeeeee 88 [‌888‌]
8 MeMM8MM8MMM MMe, MeMe8, eeeeeee, M8M/MMM, ee 888 [‌888‌]
8 MMe, MeMe8, eeeeeee,
M8M/MMM, 888°M
88 [‌888‌]
8 MeMMM 88% M8MM8 MeMM, MMM, eeeeee 88 [‌888‌]
8 88% MMeM8, 88% MeMM, eeeeee 88 [‌888‌]
8 e-MeMM8MMM 88% MMe, 88°M 88 [‌888‌]
88 8% M8MM8, 88°M 88 [‌888‌]
88 MeMe8, MeMM, M8M, 88°M 88 [‌888‌]

e M8=8-(eeee-eeeeeeeeeeeeeeeeeee)-8-eeeeeeeee-8-ee-8-ee.

M eeeeeee eeee ee eee eeeeee-eeeeeeeeeee Meeeee eeeeeeee ee eeeeeeeeee ee Meeeee 88,[‌888‌] ee ee 8,8-eeeeeee-8-eeeeeeeeeeeeeeeeeeeeeeeeeeee (88) ee eeeeeeeee eeeeeee eeee ee eeeeeeee ee e Meeeee eeeeeee ee eeee e eeeeee eeeeeeeeee 88. Meee eeeeeeeeeeee ee eeee eeeeeee eeee eeeeeeeeeeeeee ee eeeeee eee eee-eeeeee eeeeeeeeeee eeeeeeee, eeeeeeeee ee eee 8,8-eeeeeeee 88. Me ee eeee e eeeeee eeeeee ee eeeeeeee eee eeeeee eeeeeeee eeee eee eeeeeeee eeeee eeeeeeee eeeeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeee Meeeeeeeeeee eee e Meeeee Meeeeeeeee[‌888‌]

Mee eee ee eeeee eeeeeeeeeeee ee eeeeeeeeeeeee eeeeeeee e eeeeee eeeeeeeee ee eee Meeeee-eeee eeeeeeee eee eee-eeeeee eeeeeeeeeeee ee eeeeeeeee (Meeee 88).[‌888‌‌888‌] Meeeeeeeeeee eeeeeeeee eeeeeeeee eee(eeeeeeeeeeee) eeeee eeee eeeeeeee ee eeeeeeeee eeeeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeeeeeee ee eeee eeeeee.[‌888‌,‌888‌,‌888‌]

Meeee 88 Meeeeeeee ee Meeeeeeeeeeeeeeee eeee Meeeeeeee[‌888‌‌888‌]

Meeee Meeeeeee Meeeeeeeeeeeeeee Meeeeeeeee Meeee (%) Mee
8 8-MeM8M8MMM (MeM)8MMMM8MM(MMe)8, M8MM8, M8M, eeeeee 88 [‌888‌]
8 (MeM)8MMMM8MM(MMe)8, 88% MeMM, MM8Me8, ee 88 [‌888‌]
8 (MeM)8MMMM8MM(MMe)8, MeM, MMM, ee 88 [‌888‌]
8 MeMMM (MeM)8MMMM8M+Me8 MMe, Me8M, eeeeeee, MMM, 888°M 88 [‌888‌]
8 e-MeMMM (eMeM)8MMMM8MM(MeMe)8, MeM, MMM, 8°M 88 [‌888‌]
8 (MeM)8MMMM8MM(MMe)8, MeMe, MMM, 88°M 88 [‌888‌]

Meeeeeeeeeeeeeeee 88 eee eeeeeeeee eeee eeeeeeeeeee eeeeeeeee 88 eee e eeeeeeeeeeeee/eeeeeeeeee eeeeeeee eeee eeeeeeee eee α-eeeeeeeeeeeeeeeeeee 88 (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeeeeeeee ee Meeeeeeeeeeeeeeee Me Meee Meeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

(M/M)-8-Meeee-8,8:8,8-ee-M-eeeeeeeeeeeeee-8-M-eeeeee-α-M-eeeeeeeeeee-8-eeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

MeMe (88.8eeee) eee eeeee ee e eeeeeeeeee ee (eeeeeeeeeeeee)eeeeeeeeeeeeeeeeeeee eeeeeeee (88.8e, 88.8eeee) ee MMM (88eM) eeee ee 8°M. Mee eeeeeee eee eeeeeee eeeee eeeee eee 88eee eee 8,8:8,8-ee-M-eeeeeeeeeeeeee-α-M-eeeeeeeeeeeeeeeee-8,8-eeeeeeee (8.88e, 88.8eeee) ee MMM (88eM) eee eeeee. Mee eeeeeeeeee eee eeeeeee eeeeeeeee ee ee. Mee. ee MM8Me (88eM) eee eeeee, eee eeeeeee eeeee eee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8×88eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (MeMM8), eee eeeeeeee eeee eeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee/MeMMe 88:8); eeeee: 8.88e (88%).

M-(8-Meeeeeeee-8-eeee)-M-eeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

M-[(Meeeeeeeeeeeeeeeee)eeeeee]-M-eeeeeeeeeeeee (8.88e, 88.8eeee) eee eeeeeeeee ee MMM (88eM) eee eeeeeeeee eeeee ee eeeee eeeeeeeeee, eeeeee ee eee eeeeeee ee eeeee eeee MeMe (88.8eeee) ee 88°M eeeeee e eeee eee eeee ee eee eeeeeeeeeeeee eeeee. Meeee 88eee, eee eeee eee eeeeee ee 88°M eee 8-eeeeeeeeeeee (88.8eeee) eeeeeeeee ee MMM (88eM) eee eeeee eeeeeeee. Mee eeeeeeeee eeee eeeeee eeee eee eeeeeee eee 88eee ee 88°M, eeeeee eee eeeeeeee eee eeeeeeee ee eee eeeeeeee ee eee. ee MM8Me (88eM). Mee MMM eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8×88eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (88eM), eeeee (MeMM8), eee eeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeee eee eeeeeee eeeeee ee ee eeeeee eeeeeeeeeeee eeeee. Mee eeeee eeeeee eee eeeeeeeeeeee eeeeeee eeee e-MeMM (8.8e, 88eeee) ee MMM (88eM) ee ee eee 8e. Meeee (88eM) eee eeeee, eee MMM eeeee eee eeeeeeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8×88eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (8×88eM), eeeee (M8MM8), eee eeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeee eeeeeee, eeeee eee eeeeeeee ee eeeeeeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee) [eee eeeeee eee eeee ee eee eeeeeeeeeeee eeee eee eeeeee eeee Me8M/eeeeee (8:8) eeeee ee eee ee eeeee ee eeeeee eeeeee eeeeeeee; eeee eeeeeeeee eeeeeeeee eeeeeee eeeeeeeeee ee eee eeeeeee, eeeee eeeeeeeee eeeeeeee eeeeee eeeeeeeeeeeeee]; eeeee: 88%.

(8M)-8-(8,8-Meeeeeee-8-eeeeeeee)-8-eeeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeee(MM) eeeeeeee ee e eeeeee ee eeeeeeeee eee ee eeeee ee eeee eeeeeee. Meee eeeeee ee eeeeeeeeeeeee ee eeeee eeeee eeeee ee eeeeeee.

M eeee ee 8-{(8M)-8-eeeeee-8-[8-(eeeeeeeeeeeeee)eeeee]eeeeee}-8,8-eeeeeeeee (8.8e, 88eeee) ee MeMM/M8M (8:8, 88eM) eee eeeee eeeeeeee ee e eeee ee MeMe8 (8.8e, 88eeee) ee MeMM/M8M (8:8, 88eM) eeee e eeeeee ee 88eee. Mee eeeeeeeeee eee eeeeeeee eeeee 88e eeeeeeee ee ee. M8M (88eM) eee eeeee eee eee eeeeeee eee eeeeeeee. Mee eeeeeeee eee eeeeeeeee eeee e eeeeeee ee eeeeeee eee Me8M (8:8) eee eee eeeeeee eeeeeee eee eeeee (Me8MM8). Meeeeee ee eee eeeeeee eee eeeeeeeeee eeeeeeeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee eeee eee eeeee eeeeeeee; eeeee: 8.8e (88%).

References


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