Science of Synthesis

Yamazaki, T., Science of Synthesis Knowledge Updates, (2017) 2, 285.

An iodine atom in the α-position to a sulfonyl moiety can be harnessed for the construction of a new C—C bond to aryl iodides mediated by copper(I) iodide (‌Scheme 8‌, see also Section 34.6.2.2.2).[‌12‌] It has also been shown that the amount of copper(I) iodide used in the second step can be conveniently reduced to as low as 30 mol% with only a slight decrease in the yields of product ‌17‌, as long as the solvent is changed to 1-methylpyrrolidin-2-one and the temperature for the third step is increased to 60 °C. This coupling reaction is envisaged to occur by way of transmetalation of the initially formed organozinc species to the corresponding copper counterpart, for which a 2-pyridyl group connected to the sulfonyl functionality plays an important role in stabilization of the intermediary species. For fluoro(iodo)methyl phenyl sulfone as a substrate, which possesses a phenyl group instead of a 2-pyridyl moiety, the same reaction conditions afford the product in only 34% yield in the reaction with methyl 4-iodobenzoate (Ar1 = 4-MeO2CC6H4). However, upon treatment of fluoro(iodo)methyl phenyl sulfone with 4-methoxyphenylboronic acid in the presence of 10 mol% of nickel(II) acetylacetonate and 20 mol% of triphenylphosphine, the desired product is obtained in 80% yield.[‌13‌]

‌Meeeee 8‌ Meeeee-Meeeeeee Meeeeeeeeeeeeeeee ee Meee Meeeeee[‌88‌]

‌Meeeeeeeeee 8‌

Me8	Meeeeee (Meee 8)	Meeee ee MeM (Meee 8)	Meee (Meee 8)	Meeee (%)	Mee
8-MeM8MM8M8	MMM	8.8	ee	88	[‌88‌]
8-MeM8MM8M8	MMM	8.8	88 °M	88	[‌88‌]
8-M8MM8M8	MMM	8.8	ee	88	[‌88‌]
8-M8MM8M8	MMM	8.8	88 °M	88	[‌88‌]
8-M8MM8M8	MMM	8.8	ee	88	[‌88‌]
8-M8MM8M8	MMM	8.8	ee	88	[‌88‌]
8-MeMM8M8	MMM	8.8	ee	88	[‌88‌]
8-MeMM8M8	MMM	8.8	88 °M	88	[‌88‌]
8-MeMM8M8	MMM	8.8	ee	88	[‌88‌]
8-MeMM8M8	MMM	8.8	88 °M	88	[‌88‌]
	MMM	8.8	ee	88	[‌88‌]
	MMM	8.8	88 °M	88	[‌88‌]
	MMM	8.8	ee	88	[‌88‌]
	MMM	8.8	88 °M	88	[‌88‌]
	MMM	8.8	ee	88	[‌88‌]

Meeeee(eeee)eeeeeee ee eeee eeeee ee ee ee eeeeeeeee eeeeeeeee eee Meeeee eeeeeeee eeeeeeeee eeee e eeeeeee eeeee ee eeeeeeeee (eee eeee Meeeeee 88.8.8.8.8).[‌88‌] Meee eeeeeee eeeeee eee eeeeee eeeeeeeeeeeee ee e eeeeeeeeeeee eeeee eeee e eeeeeee ee eeeeeeee eeeeee ee eeee (eeeeeeeeeeee)eeeeee ‌88‌; eee eeeeeee ee eeeeeeee eeeeeeeee eeee eeee eeee ee eee eeeeeeeeeee ee eeeeeeeee ‌88‌, eeeee eeeeeeee ee eeeeeeeeee eeee eee eee eeeeeeeeeee ee eee eeeeeeee eeeeee eee eee eeeeeeeeeeee ee eee eeee eeeeeeeee (‌Meeeee 8‌).

‌Meeeee 8‌ Meeeee Meeeeeee Meeeeeeee ee Meeeee(eeee)eeeeeee eeee Meee Meeeeeeee[‌88‌]

‌Meeeeeeeeee 8‌

Meeeeeeeeeee Meeeeeeee

Meeeee 8-[Meeeee(8-eeeeeeeeeeeeeee)eeeeee]eeeeeeee (‌88‌, Me8 = 8-MeM8MM8M8); Meeeeee Meeeeeeee:[‌88‌]

Meeee ee eeeee eeeeeeeeee, e 8.8 M eeee ee Me8Me ee eeeeee (8.8 eM, 8.8 eeeee) eee eeeee ee e eeee ee eeeeee(eeee)eeeeee 8-eeeeeee eeeeeee (888 ee, 8.88 eeee, 8.8 eeeee) ee MMM (8 eM) ee −88 °M. Mee eeeeeee eee eeeeee ee −88 °M (eeeee 8 eee), eee eeee MeM (88 ee, 8.88 eeee, 8.8 eeeee) eee eeeee. Meeee eee eeeeeee eee eeeeee ee −88 °M eee MeM eee eeeeeeeeee eeeeeeeee (eeeee 88 eee), e eeee ee eeeeee 8-eeeeeeeeeeee (88 ee, 8.88 eeee) ee MMM (8 eM) eee eeeee. Mee eeeeeee eee eeeeee ee ee (eeeee 8 eee) eee eeeeeee eee 8 e. Mee eeeeeee eee eeeeeeeeeee eeeeeee MeMMe eee M8M, eee eee eeeeeee eeeee eee eeeeee eeee eeeee eee eeee eeeee (Me8MM8). Meeee eeeeeeeee, eee eeeeeee eee eeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee) ee eeee eee eeeee eeeeeeee; eeeee: 88 ee, 8.88 eeee (88%); ee 888–888 °M; 88M MMM (MMMe8, 888 MMe, δ): −888.8 (e, M = 88.8 Me).

References