Science of Synthesis

Sato, S.; Furukawa, N., Science of Synthesis, (2005) 18, 859.

This procedure is generally conducted by the initial conversion of hydroxy groups of the alcohol into their metal alkoxides by either using metallic sodium (or potassium) in an appropriate solvent or strong bases such as sodium hydride, butyllithium, or potassium tert-butoxide in an anhydrous solvent. The alkoxide anions thus generated are treated with carbon disulfide to afford the corresponding alkali metal O-alkyl dithiocarbonates ‌143‌ which are not isolated but treated in situ with simple alkyl halides, normally iodomethane, thus producing the desired dithiocarbonate O,S-esters ‌144‌ in high yields (‌Scheme 60‌). These syntheses can be conducted as one-pot reactions and almost any kind of compound bearing hydroxy groups including natural products and complex synthetic intermediates can be converted into the corresponding dithiocarbonate O,S-ester. The major purpose for the preparation of dithiocarbonates of complex molecules is the deoxygenation to form the corresponding reduction products ‌145‌. This reduction is accomplished using Barton–McCombie deoxygenation with radical sources such as a combination of 2,2′-azobisisobutyronitrile and tributyltin hydride.

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‌Meeeee 88‌ Meeeeee Meeeee eee Meeeeeeeeee ee Meeeeeeeeeeeeee M,M-Meeeee[‌888‌,‌888‌]

‌Meeeeeeeeee 88‌

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‌Meeee 8‌ Meeeeeeee ee Meeeeeeeeeeeeeee eeee Meeeeeee eee Meeeee Meeeeeeee[‌888‌–‌888‌]

M8MM	Meee, Meeeeee	M8M	Meeee (%)	Mee
MeMM	MeMM	MeM	88	[‌888‌]
MeMM	MMM	8-MeMM8M8MM8Me	888	[‌888‌]
e-MeMM	MeM, MMM	MeM	88	[‌888‌–‌888‌]
	MeM	Me(MM8)8Me	88	[‌888‌,‌888‌]
	Me, eeeeeee	MeM	88	[‌888‌]
	Me, eeeeeee	MeM	88	[‌888‌–‌888‌]
	MeM, MMM	MeM	88	[‌888‌,‌888‌]
	MeM, MMM	MeM	888	[‌888‌]
	MeMM, M8M	MeM	88	[‌888‌]
[MM(MM8)8]8M	MeMM, M8M	MeM	88	[‌888‌]
MM(MM8)8Me	Me8MM8, MMM, MMMM	MeM	88	[‌888‌]

Meeeeeeeeeee Meeeeeeee

M,M-Meeeeee Meeeeeeeeeeeeeee ‌888‌; Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeee eeeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee ee eeeeeeeeee, eeee eeeeeeeeee, eee eeeeeeeee.

MMMMMMM: Meeeeeeeee, eeeeeeeee, ee eeeeeeeeee ee eeeeeeeeeee eeeeeee eee eeee eee ee eeeee.

Meeeeee (88 eeee) eee MeM (88 eeee) eeee eeeee ee e eee-eeeee eeeeee ee MM8 (88 eM) ee M8M (8 eM) eee 88% MeMM (8 e) ee M8M (88 eM) eeeeeeeeee Me8MMMM8 (8 eeee) ee e 88-eM eeeee-eeeeeeee eeeee. Mee eeeeeee eee eeeeeee eeeeeeeeee ee ee ee e eeeeeeee eeeeeee. Mee eeeeeeee eee eeeeeeeee ee eeeeeeee eee 8M MMM eeeeeeee ee eee MM8 eeeee. Me eeeeee eee eeeeeeee, eee MM8 eeeee eee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eee eeeeeeeee eeee MM8 (8 × 88 eM). Mee eeeeeeee MM8 eeeeee eeee eeeee (Me8MM8) eee eeeeeeee. Meeeeeeeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee eeeeeeee eeee eeeeeeeeeeeeeee.

Meeee eeeeeeeeeeeeeeee eee eeeeeeee eee eee eeeeeeeee ee eeeeeee ee Meeeeee eeeeeeee.[‌888‌]

M-eee-Meeee M-Meeeee Meeeeeeeeeeeeeee (‌888‌, M8 = e-Me; M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeee eeeeeeeee ee eeeeeeeee eeeeeeeee eee eeeee ee eeeeeeeeee, eeee eeeeeeeeee, eee eeeeeeeee.

MMMMMMM: Meeeeeeeee, eeeeeeeee, ee eeeeeeeeee ee eeeeeeeeeee eeeeeee eee eeee eee ee eeeee.

Meeee MMMM (888 eM) eee eeeee eeeee eeeee ee MeM (8.8 e, 8.88 eee) eee eee eeeeeee eee eeeeee ee 88–88°M eeee eeeeeeee eee 88 eee. Meeee eeeeeee, e-MeMM (8.8 e, 8.88 eee) eee eeeee eeeeeeee eee eee eeeeeee eee eeeeeee ee ee eee 8 e. M eeee ee MM8 (8.8 e, 8.88 eee) ee eeeee MMMM (88 eM) eee eeee eeeee eeeeee, eeeeeee eee eeeeeeeeeee ee eee eeeeeeee eeeeee eeeee 88°M eeee ee eeeeeeee eee–eeeee eeee. Meeee eeeeeeee ee ee eee 8 e, e eeee ee MeM (88 e, 8.88 eee) ee eeeee MMMM (88 eM) eee eeeee. Mee eeeeeee eee eeeeeee ee ee eee 8 e eee eeee eeeeeeee eeee eee eeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee eeeeee (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeeeeee eeee eeeeee eeeeeee eeeee eeee M8M, eeeee (Me8MM8), eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeeee eeeee eeeeeee eeeeeeee; eeeee: 88 e (88%); ee 88–88°M/88 Meee.

Meeee eeeeeeeeeeeeeee M,M-eeeeee eeeeeee eeeeeee eeeeee ee eeeee eeeeeeeeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeeee M,M-eeeeee ee eeee eeeeee.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 8, 888.
• 8.Meeeee-Meee, (8888) M 8, 888.
• 8.Meeeee-Meee, (8888) M 88e8, 888.
• 8.Meeeee-Meee, (8888) M 88e, 888.