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

DOI: 10.1055/sos-SD-025-00180

Lindenschmidt, A.Science of Synthesis, (200725262.

Silyl groups have the ability to stabilize an adjacent carbonmetal bond, facilitating, for example, deprotonation with an alkyllithium base.[‌200‌] Several methane-derived reagents 37 bearing a silyl group and possibly one or two additional substituents have been developed.[‌200‌‌206‌] For example, an activated species such as the lithium salt 38 can be employed in the one-carbon homologation of aldehydes (see Scheme 17), and, in the first step of the homologation sequence, a heteroatom-substituted vinylic intermediate 39 is generated from the aldehyde via a Peterson-type alkenation. This intermediate is then hydrolyzed to the homologated aldehyde 40.

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Meeee 88 Meeeeeeeeee ee Meeeeeeeee-Meeeeeeeeee Meeeeee[‌888‌,‌888‌,‌888‌,‌888‌‌888‌]

Meeee M8 M Meeeeeeeee Meeee (%) Mee
8 Me MMM [Me],e eeeeeee, 88°M 88 [‌888‌]
8 8-MeMM8M8 MMM 8. MeMM8MMM, eeeeeee, ee
8. Me(Me)8MM8MeMe8Me, eeeeeee, ee
88 [‌888‌]
8 (M)-MMe=MMMe MMM (MMM)8MMMMM, MMMM,e MMM, 88°M 88 [‌888‌]
8 MMe=MM8 MeMe8Me [(MeMe8Me)8MM]Me,e Me8M, 88°M ee ee eeeee [‌888‌]
8 (MM8)8Me MMM MMM8, Me, MMMMe, MeMe8 (eee.), MMM, 88°M 88 [‌888‌]
8 MMM MMMMMMe8, MeMe8, MMM, 88°M 88 [‌888‌]
8 MMM MMMMMMe8, MeMe8, MeM, ee eeeee, MMM/MMM, 88°M 88 [‌888‌]
8 MMe (MMM)8MMMMe, MMMM,e MMM, 88°M 88e [‌888‌]
8 MMe 8. [MMMMMMMe]Me, MMM, 88°M
8. MM, MMM, 88°M
88 [‌888‌]
88 e-Me M(M)(MMe)8 (MMM)8MMMM(MMe)8, MMMM,e MMM, 88°M 88 [‌888‌]
88 eMe M(M)(MMe)8 (MMM)8MMMM(MMe)8, MeMe, MMM, 88°M 88 [‌888‌]

e [Me]=eeee(eeeeeeeeeeeeee)eeeeeeeeeeeeeeeee.

e [(MeMe8Me)8MM]Me=[eee(8-eeeeeeeeeeeeeeeeeeee)eeeeee]eeeeeee.

e MMMM=eeee(eeeeeeeeeeeee)eeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeeeee.

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Meeeee 88 Meeeeeeeeeee eee Meeeeeeee Meeeeeeeeeeee[‌888‌]

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Meeeee 88 Meeeeeeeee ee Meeeeeeeeeee eeee Meeeeeeee[‌888‌]

Me eeee eeeee, eeeeeeeeeee ee eeeeeeee ee eeeeeeeee ee eee eeeeeeeeeee eeee 8-eeeeeeeeeeeeeeeeeee eeee.[‌888‌,‌888‌] Meeeeee, eeeeeeeeeee eeeeeee eeee ee eeeeeeeeeee eeeee Meeeeeeee eeeeeeeeee, ee eeee eeeeeeeeeeeeeeeee eeee eeee eeee.[‌888‌‌888‌] Meeeeeeeee eeeeee, eeeeeeeee eeeeeeeeee eeee eeeeeee eeeeee, eeeeeee, eee eeeeee eee eee eeeeeeeee. Meeeeeee eee eee eeeeeeeeee ee eeeeeeee(eeeee)eeeeeee eeee α,β-eeeeeeeeeeee eee eeeee ee Meeee 88.[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌]

Meeee 88 Meeeeeeeeee ee Meeeeeeeeeeeeeeeeeee[‌888‌,‌888‌,‌888‌,‌888‌,‌888‌]

Meeee Meeeeeeeeee α,β-Meeeeeeeeee Meeeeeeeee Meeee (%) Mee
8 MMMMM, MM8Me8, 8°M ee ee 88 [‌888‌]
8 MMMMM, MM8Me8, ee 88 [‌888‌]
8 MMMMM, MM8Me8, ee 88 [‌888‌]
8 e-MeMMM, Me(MeMe)8, M-(+)-MMMM, MM8Me8, 88°M 88 [‌888‌]
8 MMMM,e eeeeeee, ee 88 [‌888‌]

e MMMM=eeeeeeeeeeeeeeeee.

Meeeeeeeeeee, eee α,β-eeeeeeeeeee ee eeeeeeeeee ee eee eeeeeeee eeeee eeeeee eeeeeeeeee eeee, eee eeeeeee, eeeeeeeeee, eeeeeeee, ee eeeeee eeee.[‌888‌‌888‌,‌888‌‌888‌] Meeeeeee eeeeeeeeee eeeee ee eee Meeee eeee eeeeeee eeeee eeeeeeeeeeeeeeeeee eeeee eeee eeee eeee eeeeeeeee.[‌888‌] Meeeeeeee, eeeee eeeeeeeeee eeeeeeeeee eeee eeee Meeee eeee, eee eeeeeeee ee eeeeeeee ee eee eeeeee, e eeeeeeeeeee eeeeeeeeee eeee eee ee eeeeee ee eee eeeeee ee e eeeeeeeee eeeeeeee.[‌888‌,‌888‌] Meeeeeeeeeeeee eeeeeeee ee eeee eeeeeeeeee eeee eeeeeee eeee eeee ee eeeeeeeeee eee eeeeeeeeee ee Meeee 88.[‌888‌‌888‌,‌888‌,‌888‌] Meeee eeeeeee ee eeeeeeeeeee eee eeeeeeeee eeeeeeee eeee eee α,β-eeeeeeeeeeee ee eeeeeeeee eeeeee.[‌888‌] M eeeeee eeeeeeeee ee eee eeeeeeee eeeeeeeeee eeeeeeee eee eeeeeeee eeee eee α,β-eeeeeeeeeee ee eee eeee ee eee eeeee eeee eeeee.[‌888‌]

Meeee 88 Meeeeeeeee ee α,β-Meeeeeeeeeee ee Meeeeeeee[‌888‌‌888‌,‌888‌,‌888‌]

Meeee α,β-Meeeeeeeeee Meeeeeee Meeeeeeeee Meeee (%) Mee
8 MMeM8, MMM/M8M, ee e.e.e [‌888‌]
8 MMeM8, MMM/M8M, ee eeeee [‌888‌]
8 8. M8MM8, MeMM, eeeeee
8. 88% MeMM, ee
88 [‌888‌]
8 Me(MM8)8MM8MMM MMeM8, MMM/M8M, ee 88 [‌888‌]
8 MeMM8MM(MMe)8 MM8MMe8, 88% MeMM/M8M, 88°M 88 [‌888‌]
8 MM8MMe8, eee MeMM, 88°M 88 [‌888‌]

e e.e.=eee eeeeeeee; eee eeeeeeee eeeeeee eee eeee eeeeeeee ee e eeeeeeeeee eeeeeeeeeeeeee.

Meeeee(eeeee)eeeeeee ee eeee(eeeee)eeeeeee 88 eee ee eeeeeeee eeeeeeeee eeee eee eeeeeeeeeee eeeeeeeee 88 eeeee Meeee eeeeeeeee eeeeeeeeee (Meeeee 88).[‌888‌‌888‌] Meeeeeee eeeeeeee eeeeeeee ee eeeeeee eeee, eeeeeeeeeeeeee M-eeeee eee eeee ee eeeeeeee.[‌888‌] Meeeeeeeee ee eee eeeeee ee eee eeeeeeeee eeeee e eeeeeeeeeeee eee eeee eeeeeeeeeeeeee ee eee eeeeeeee ee ee eeeee eee eeeeee- ee eeeeeee-eeeeeeeeeee ee eee eeeee eeeee. 8-Meeeeee(eeeee)eeeeeee 88 eee, eeeeeee, ee eeeeeeeee.[‌888‌] Me eee eeeee eeee eeee eeeee ee eeeeeeeeeee eeee eee eeeeeeeeeeeee eeeeeeee ee eee eeee, eeee eeeeeeee eeeeeeee ee eeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeeee eee e eeeeeeeee. Meeee eeeeeeeeeeeee ee eeee eeeeeee eeeeeee eeee eee eeeeeeeeeeeee eeeeeee(eeeee)eeeeee ee eeeeee ee ee eeeeeeeeeeee ee eee eeeeeeee.[‌888‌,‌888‌] 8-Meeeeee(eeeee)eeeeeee eee ee eeeeeeee eeee eee eeeeeeee eeeeeeeee ee eeeeeeeee eeeeee eee eee ee eeeeee eeeeeeeeee, eeeeee eeee eeee eeeeeeeeee eeeeeeeeeeeee ee e eee-eeeeee eeeeeeeeeeee eeeeeeee ee eeeeeeeee. Meeee eeee(eeeee)eeeeeee, eeee ee eeeeee(eeeee)eeeeeee 88 ee eeeee(eeeee)eeeeeee 88, eeee ee ee eeeeeeeeeee eeee ee eeeeeeeee eeeeeee eeeee, eeeeeeee eee eeeeeee ee eee eeeeeeeeeeeeee ee e (eeeeeeeeeeeeee)eeeeee eeee ee eeeeeeee eee eee eeeeeeeeeee/eeeeeeeeee eeeee eee eeee eeeeeeee.[‌888‌] Meee(eeeee)eeeeeee eee ee eeeeeeeee eeeee Meeeeee eeeeeeeee eeeeeeeeee eeee eee eeeeeeeeeeeee eeeeee(eeeee)eeeeeee ee eeeeeeeee eeee eeeee eeeeeeeeeeeeeeeee eeee eeeeeee ee eeeeeeeeeeeeeeee eeeeeeeeeee eeeee eeeeeee ee eeeeeeeeeeeeeee.[‌888‌‌888‌] Meeeeeeeee eeeeeeeee eeeeeeeeee ee eee eeeeeeee eee ee eeeeeeee eeeeee eeee eeeeeeee eeeeeeee ee 8-eeeeeeeeeeeeeeeeeee eeee. Meeee(eeeee)eeeeeee 88 eee ee eeeeeeeee eeee eeeeeeeee ee e eeeeeee eeeeeeee eeeeeeee eeeeeeeee eeeee e eeeeeeeeeee ee eeeeeeeee eeeeeeee eeeeeeee eee eeeeee eeee eee eee eeeeeeeeee eeee, eee eeee eeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeeeee eeeeeeee eee eee eeeeeeeee.[‌888‌]

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

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeee (Meeee 88, Meeeeee 8, 8, eee 88); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee eee eeeeeeee (8eeee) eee (MMM)8MM (888ee, 8.8eeee) eeee eeeee ee eeeee MMM (8eM) eeeeeeeeee 8-Å eeeeeeeee eeeeee eee eee eeeeeee eee eeeeeeee. Meee, e eeeeeeeee eeeeee ee eeee(eeeeeeeeeeeee)eeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeeeee (88% eeeee.) eee eeeee. Meeee eeeee eeeeeee ee eeeeee eee 88e, eee eeeeeee eee eeeeee eee eeeeeee eeee MM8Me8, eeeeee eeeee eeeeee eeee 8.8M ee MMe, eee eeee eeee M8M. Mee eeeeeee eeeee eee eeeeeeeee eee eeeee. Meeeeeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeeeeeeee, eeeee eee eeeeeeee ee Meeeeeeee eeeeeeeeeeee. Mee eeeeeeeeee ee ee eeeeeeee eeee e eeeee eeeeeeeeeee eeee M,M-eeeeeee [eee(eeeeeeeeeeeeee)eeeeee]eeeeeeeeeee, ee eeee e eeeee eeeeeee eeee (eeeeeeeeeeeeee)eee(eeeeeeeeeeeeee)eeeeeee eee eeee eeeeeeeee ee eeeeeee eeee.

Meeeee 8-Meeeee-8-[8-(eeeeeeeeeeeeee)eeeeee-8-ee]eeeeeeeeeeeeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

88% MMMMM (888ee, 8.8eeee) eee eeeee ee e eeeeeee eeee ee eeeeee 8-eeeeee-8-[(M)-8-(eeeeeeeeeeeeee)eeeee]eeeeeeeeeeeeeeeeeeeeeee (888ee, 8.8eeee) ee MM8Me8 (88eM) eeee ee 8°M. Mee eeee eee eeeeeee ee eeee ee ee, eee eeee ee eee eeeeeee eee 8e. Mee eeeeeee eeeeeeee eee eeeeee eeeeeee e eeeee eeeeee eee eeeeee (MeMMe). Meeee eeeeeeeeeeeee ee eee eeeeee, eee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee ee eeeeee eee eeeee eeeeeeee ee e 8:8 eeeeeee ee eee eeeeeeeeeeeee; eeeee: 888ee (88%).

Meeeee 8-(8-Meeeeeee)-8-eeeeeeeeeeeeeeeeeeeeeeeeeeeee (Meeee 88, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee eeeeee 8-eeeeee-8-[8-(eeeeeeeeeeeeee)eeeeee-8-ee]eeeeeeeeeeeeeeeeeeeeeee (888ee, 8.88eeee) eee 88% MMeM8 (8.8μM) ee 88% ee MMM (8eM) eee eeeeeee eee 88e. Mee eeeeeee eee eeeeee eeeeeee e eeeee eeeeee eee eeeeee (MeMMe). Meeee eeeeeeeeeeeee ee eee eeeeee, eee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee ee eeeeee e eeeeeeeee eee; eeeee: 88ee (888%).

References