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You are using Science Of Synthesis as a Guest. Please login or sign up for a free trial to access the full content. Carbonylation and Alkenylation

DOI: 10.1055/sos-SD-209-00407

Kalyani, D.; Desai, L. V.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (20133752.

The preceding sections detailed transformations involving the coupling of sp3 C—H bonds with arylating reagents. Examples of palladium-catalyzed carbonylation and alkenylations of unactivated sp3 C—H bonds have also been developed as alternative methods to construct C(sp3)—C bonds. Early reports by Fujiwara demonstrated the first examples of the palladium-catalyzed C(sp3)—H carbonylation of alkanes.[‌93‌‌95‌] The carbonylation of simple alkanes, such as ethane, is achieved using a palladium(II) acetate/copper(II) acetate dual catalyst system under a carbon monoxide atmosphere (20–50 atm) with potassium persulfate as the terminal oxidant and trifluoroacetic acid as the solvent. Although the carboxylic acid products of this transformation are efficiently obtained, these reactions are limited by the use of excess substrate and high carbon monoxide pressures (Scheme 37).

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Meeeee 88 Meeee ee Meeee-Meeeeeee M—M Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

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Meeeee 88 Meeeeeee Meeeeeeee ee Meeee-Meeeeeee M—M Meeeeeeeeeeee[‌88‌]

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Meeeee 88 Meeeeeee Meeeeeeee ee M—M Meeeeeeeeeee eee eee Meeeee ee ee M-Meeeeeeeee Meeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
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M8M8 88 [‌88‌]

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Meeeee 88 Meeee ee Meeee-Meeeeeee M—M Meeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 Meeee (%) Mee
Me 8,8-Me8M8M8M(MM8)8 M 88 [‌88‌]
Me (MM8)8MM8Me M 88 [‌88‌]
Me M M 88 [‌88‌]
Me MM8 88e [‌88‌]

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Meeeee 88 Meeeee Meeeeeeee eeee Meeeeeeeee Meeeeeeeee α-Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
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Me 88 [‌88‌]

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Meeeeeeeeee 88

M8 M8 M8 Meeee (%) Mee
Me M MMe 88 [‌88‌]
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M MM8 MMe 88 [‌88‌]
M M Me 88 [‌88‌]
M M MM 88 [‌88‌]
M M MMe8 88 [‌88‌]

Meeeeeeeeee 88M

M8 ee Meeee (%) Mee
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Meeeee 88 Meeeeeeeee ee Meeeeeeeeeeeeeeeeee Meeeeeee eeee Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
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Me 88 [‌88‌]

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M-[8,8,8,8-Meeeeeeeeee-8-(eeeeeeeeeeeeeee)eeeeee]eeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

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8,8-Meeeeee-8M-eeeeeeeee-8-eee Meeee 88; Meeeeee Meeeeeeee:[‌88‌]

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