Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
25.1.12.2.4 Variation 4: Using Stoichiometric Amounts of Carbonylferrate Salts and an Acidic Workup

DOI: 10.1055/sos-SD-025-00209

Hashmi, A. S. K.Science of Synthesis, (200725329.

Commercially available disodium tetracarbonylferrate (44),[‌120‌] for which an excellent preparative procedure is available,[‌121‌] can be used instead of a carbonylhydridoferrate, but the acyl complex that is formed after alkylation is anionic, and acid treatment is required to liberate the aldehyde 45 (Scheme 12).[‌122‌] Triphenylphosphine can also be added to facilitate the workup.[‌121‌] Ester groups on the substrate are tolerated.[‌122‌] Electrochemical reduction of pentacarbonyliron(0) in acetonitrile, followed by the subsequent addition of an alkyl halide and an acid, also gives the corresponding aldehyde.[‌123‌] Detailed studies have been made of both the oxidative addition[‌124‌] and the alkyl migration[‌125‌,‌126‌] steps in the reaction of the ferrates with alkyl halides.

Meeeee 88 Meeeeeeee eeee Meeee Meeeeeee eee Meeeeeeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeeee 88

M8M Meee/Meeeeeee Meeee (%) ee 88 Mee
Me(MM8)8Me MeMM/Me8M 88 [‌888‌]
Me(MM8)8Me MeMM/Me8M 88 [‌888‌]
Me(MM8)8Me MeMM/Me8M 88 [‌888‌]
MeMM8Me MeMM/Me8M 88 [‌888‌]
Me8M=MMMM8MM8Me MeMM/Me8M 88 [‌888‌]
Me(MM8)8MM(Me)Me MeMM/Me8M 88 [‌888‌]
MeM8M(MM8)8Me MeMM 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeee 8-Meeeeeeeeeeee [88, M8=(MM8)8MM8Me]; Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeee eeeeeeee ee eeeeeeeee eeeeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee eee eeeeeee eeee ee e eeee.

MMMMMMM: Meeeeeeeeeeeeeeee(8) ee e eeeeeeeee eeeeeeee. Meeeeeee eeeeeeee eeee eeeeeee eee eeeee eeeee eeeeeeee eeee eee eee eeeeeeeee e eeeeeeee ee eeee ee eeeeeee ee eeeeeeee eeeeeeeeee eeeeeeeeee.

M eee, 8-M, eeeee-eeeeee, eeeee-eeeeeeee eeeee, eeeeeeee eeee e eeeeeeeeee eeeeeee, e eeeeee eeeeeeeee, eee e eeeee-eee eeeeeeee eeee eee eeeeee eeeeeeeee ee e eeeeee ee M8, eee eeeeeee eeee eeeeeeee eeeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeee[‌888‌] (88.8e, 888eeee) eee eee eeeeeeeeeeee MMM (8.8M). Mee eeeeeeeeee eee eeeeeee eeeeeeeeee eeeee eeeeee 8-eeeeeeeeeeeeee (88.8e, 888eeee) eee eeeee ee eee eeeeeee ee eeeeeee. Mee M8 eee eeeeeee eeee eee eeeee eeee MM eeeeeee eee eeeee eeeeee ee eee eeeee-eee eeeeeeee, eee eee eeeeeeeeee eee eeeeeee eeeee 8.888MMe ee MM eee ee eeeee 88e eeeee eee eeeee eeeeeeeee. M eeeee eeee ee M8 eee eeeeee eeeeeee eee eeeee eeeee eee eeeeee eee eeeeeee eee eeeeeeee eeeeeee eeee e eeeeeeee-eeeeeeeeee eeeeeeee eeeeee. Mee eeeeeeee eeeeee eee eeeeeee eeee M8 eee eeeeeee eeee eeeeeee MeMM (88eM). Mee MeMM eee eeeee eeeeeeee ee eee eeeeee eeee ee eee eeeee, eee eee eeeeeee eee eeeeeee eee 88eee ee eeee e eeee eee eeee, eeeee eee eeeeeeeeeeee ee eeeee 888eM ee e eeeeee eeeeeeeeee ee e eeee [MMMMMMM: Meee Me(MM)8 ee eeeeeee]. Mee eeee eee eeeeee eeee M8M (8M) eee eee eeeeeee eee eeeeeeeee eeee Me8M (8×888eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee M8M (888eM) eee eeeee eeee 8M MMe (888eM). MeMe8 (88e) eee eeeee ee eeeee eeeeeeee, eeeee eeeeeeeee ee MM eeeeeeee eee eee eeeeeee eeeee eeeeee eeeee. Mee eeeeeee eeeee eee eeeeee eeeeeeeeeeee eeee 888-eM eeeeeeee ee 8M MMe, M8M, eee. ee MeMMM8, eee eee. eeeee, eeeee (Me8MM8), eee eeeeeeeeeeee ee e eeeeee eeeeeeeeee ee eeee e eeeee eee. Meee-eeeeeeeeee eeeeeeeeee eeee eeeeeee ee eeeee eeeeeeeeeeeeee [8×88ee eeeeee, eeeeee (8M) eeee Me8M/eeeeee 8:8 (8M)]. Mee Me8M/eeeeee eeeee eee eeeee (MeMM8) eee eeeeeeeeeeee ee eeee ee eee eeee eee eeeeeeeee eeeeeee e 88-ee Meeeeee eeeeee ee eeeeeee eeeeeeee; eeeee: 88.8e (88%); ee 8888°M/8.8Meee.

References