Science of Synthesis

Whitehead, A.; Sieck, S. R.; Mukherjee, S.; Hanson, P. R., Science of Synthesis, (2005) 21, 908.

While Swern and analogous oxidations are known to be viable nonmetal routes to acylphosphonates,[‌5‌–‌7‌] alternative routes have been reported. Alkylation of (dialkoxyphosphoryl)dithianes such as ‌3‌ under basic conditions provides substituted masked oxo phosphonates ‌4‌ (‌Scheme 2‌).[‌8‌] Hydrolysis of the dithioketals ‌4‌ with bromine and silver nitrate in aqueous acetonitrile gives an array of acylphosphonates ‌5‌ in good yield. This method provides a mild, nonthermal alternative to metal-promoted oxidations (see Section ‌21.14.1.1.3‌) allowing for broad functional group compatibility.

‌Meeeee 8‌ Meeeeeeeeeeeeeee ee Meeeeeee Meeeeeeeee, Meeeeeee ee Meeeeeeeee[‌8‌]

‌Meeeeeeeeee 8‌

M8	Meeee (%) ee ‌8‌	Meeee (%) ee ‌8‌	Mee
Me	88	88	[‌8‌]
Me	88	88	[‌8‌]
(MM8)8Me	88	88	[‌8‌]
(MM8)8MM=MM8	88	88	[‌8‌]
Me	88	88	[‌8‌]
MM8MM8Me	88	88	[‌8‌]
	88	88	[‌8‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee Meeeeeeeeeeeeeee ‌8‌; Meeeeee Meeeeeeee eeee Meeeeeee ‌8‌:[‌8‌]

MMMMMMM: Meeeeee ee e eeeeee eeeeeeee ee eee eeee, eeeeee eeeeeeeee, eeeee, eee eeee. Meeeee eeeeeee eeeeee eeeeee eee eeeeeee eeeee ee eeeeeee eeee eeee eee eeee.

M eeeeeeeeeeee eeeeeeeee eeee ee MMM ee eeeeee/MMM (8.88 eee) eee eeeee ee e eeeeeee eeee ee eeeeeee 8,8-eeeeeee-8-eeeeeeeeeeeee (‌8‌; 8.88 e, 8.88 eee) ee MMM (88 eM) eeeeeeeeee eeeee eeeeeeeee eeeeeeeeee ee −88°M. Meeee 8 eee eee eeeeeeeeee eeeee eee eeeee (8.88 eee) eee eee eeeeeee eee eeeeeee eee 88 eee eeeeee eeeee eeeeee ee ee. M8M (88 eM) eee eeeee, eee eee eeeeeee eeeeeeee eeee eeeeeeeee eeee Me8M (8 × 88 eM) eee eeeee (MeMM8). Mee eeeeeeeeeeee eeeeeee ‌8‌ eee eeeeeeee ee eeeeee eeeeeeeeeeeeee; eeeee: 88–88%.

MeMM8 (8.888 e, 8.8 eeee) eee eeeee ee e eeeeeee eeee ee Me8 (8.88 e, 8.8 eeee) ee MeMM (88 eM) ee 8°M eee eee eeeeeee eee eeeeeee ee eeee e eeeeeeeeee. M eeeeeee ee MeMM (8 eM) eee M8M (8 eM) eee eeeee, eeeeeeee ee eee eeeeeee 8-eeeee-8,8-eeeeeee-8-eeeeeeeeeeeee ‌8‌ (8.8 eeee). Mee eeee eee eeeeeee eee 88 eee ee 8°M eee eeee eeeeeee ee eeee ee ee eee eeeeeee eee ee eeeeeeeeee 88 eee. Mee eeee eee eeeeeeee eee ee eee eeeeeeee eee eeeee 88% ee MM8MMe (88 eM) eee 88% ee Me8M8M8 (88 eM). Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8 × 88 eM) eee eee eeeeeeee eeeeeeee eeee eeeeee eeee eeeee (88 eM) eee M8M (88 eM), eee eeeee (MeMM8). Mee eeeeeee ‌8‌ eee eeeeeeee eeee eeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee; eeeee: 88–88%.

References