Science of Synthesis

Takeda, T.; Tsubouchi, A., Science of Synthesis, (2007) 30, 163.

Thiophilic addition of Grignard reagents to dithiocarboxylates produces sulfur-stabilized organomagnesium species ‌76‌ (‌Scheme 49‌). The subsequent reaction of ‌76‌ with various electrophiles provides a versatile method for the preparation of unsymmetrical as well as symmetrical acyclic dithioacetals ‌77‌ and ‌78‌.[‌199‌–‌201‌] This method is applicable to a wide variety of dithiocarboxylates, including aliphatic, aromatic, and α,β-unsaturated ones.

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeee ee eee Meeeeeeeee Meeeeeee ee Meeeeeee Meeeeeee ee Meeeeeeeeeeeeeeeee[‌888‌–‌888‌]

α-Meeeeeeeeee eeeeeeeeeeeee ‌88‌, eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeeeeee eeeeeee, eeeee eeee eeeeeee eeeeeeeeeeeee eeee ee eeeeeeeee, eeeeeee, eeeeeeeee eeeee, eee eeeeee eeeeeee, ee eeee ee eeeeeee eeeeeee, ee eeee e eeeeeee ee eeeeeeeeeeeeee eeeeeeeeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeeee Meeeeeeeeeeee ee eee Meeeeeee ee Meeeeeeeeeee eeee Meeeeeee Meeeeeee eee Meeeeee Meeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

M8	M+	M	Meeee (%)	Mee
Me	eeeeeee	MMe8MM	88	[‌888‌]
Me	eeeeeeeeeeeeee		88	[‌888‌]
Me	eMeMMM	MM(MM)eMe	88	[‌888‌]
Me	MeMMM	MM(MM)Me	88	[‌888‌]
Me	M8M	M	88	[‌888‌]
Me	MeMM8Me	MM8Me	88	[‌888‌]
Me	MM8	MM8M	88	[‌888‌]

Meeeeeeeee eeeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeeeeee eeeeee eee 8-(M-eeeeee-M-eeeeeeeeeee)eeeeeeee eeeeeeeeeee e eeeeeeeeee eee eee eee eeeeeeeee ee α-eeeeee eeeeeeeeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌,‌888‌]

‌Meeeee 88‌ Meeeeeeee ee α-Meeeee Meeeeeeeeeeee ee Meeeeeee ee Meeeeeeeeeee eeee Meeeeeee Meeeeeee Meeeeeee ee Meeeeeeee eeee 8-(M-Meeeee-M-eeeeeeeeeee)eeeeeeee[‌888‌,‌888‌]

β-Mee eeeeeeeeee eee eeeeeeeeeee eeee 8-eeeeeeeeeeeeeeeeeeeee eeeeeeeeeeeee ‌88‌ ee eee eeeeeeeeeeeeee eeeeeeeeeeeee eeeeeeee ee eee eeeeeeee eeeee ee eee eeeeeeeeeeee eeeeeeeee eeeeeee eeeeeee eeee β-eee eeeeeeeeeeee eee eeeeeeeeeeeeee eeeeeee (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee 8-Meeeeeeeeeeeeeeeeeeee Meeeeeeeeeeee ee Meeeeeee ee β-Mee Meeeeeeeeeee eee Meeeeeeeeeeeee Meeeeee[‌888‌]

Meee eeeeeee eeeeee ee eeeeeeee eeeee eee eeeeeeeeeeee eeeeeee eeee Meeeeeee eeeeeeee eee eeeeeeeeeee, eeeeeeeeeeeee ‌88‌ ee α,β-eeeeeeeeeee eeeeeee eee eeeeeeee eee e [8,8]-eeeeeeeeeee eeeeeeeeeeeee ee eee eeeeeeeeeeee eeeeeeeeeeeeeee eeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌] Meeeeeeee, α-eeeeeee eeeeeeeeeeeee ‌88‌ eee eeeeee ee e [8,8]-eeeeeeeeeee eeeeeeeeeeeee ee eee eeeee eeeeeeeee eeeeeeeeeeee eeeeeeeeeeeee ‌88‌, eeeeeee eeee M-eeeeeeeeeee eeeeeeeeeeee ee eee eeeeeeeeee eeeeeeee ee eeeeeeeeeeeeee eeeeeee eeeeeeee ee eeeeeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeee ee Meeee eee Meeeeee Meeeeee eee e [8,8]-Meeeeeeeeee Meeeeeeeeeeee ee Meeeeeeeeeeeeee Meeeeeeee Meeeeeeee eeee Meeeeeee Meeeeeee eee Meeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeeeeee eeeeeeee eeee ee eeeee-, eeeeee-, eee eeeeeeeeeeee eeeeeeeee eee eeee eeeeeeee eee eee eeeeeeeeee ee eeeeeeeeeeee eeee eeeeeeeeeeeee. Meeeeeeeee eeeeeeeee ee 8,8-eeeeeeee-8(8M)-eeeeeee eeee eeeeeeeeeeee eeeeeeee eee eeeeeee eeeeeee eeeeeee 8-(eeeeeeeeeeeee)-8,8-eeeeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌,‌888‌] Meeeeeee-8-eeeeeeeeeeee eeeeeeeeeeeee ‌88‌ eee eeeeeeeee eeeeeeee eee eee eeeeeeee ee eeeeeeeeeeeeeeeeeeeeeeeeee eeee eeeeeeeeeeee eeeeeeee.[‌888‌] Me eeee eeeeeeeee, eeeeeeeeee eeeeeeee eeeeeeeeeeeeee eeeeeeee, eeeeeeee ee eeeeeeeeeeeeeee ee eee eeeeeeeee, eee eeeeeeeeeeee eeeeeeee.

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeee ee eee Meeeeeeeee Meeeeeee ee Meeeeeeeeeee Meeeeeee ee Meeeeeee Meee Meeeeeeeeee[‌888‌–‌888‌]

Meee eeeeeeeeeeee eee eeeeeee eeee eeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeeeeeee eeeeeeee, eeeeeeeeee eeeeeeeeee eeeeeeee ee eeeeee eee eeeeeeeeeee eeeeeeeeeeeee ‌88‌ (‌Meeeee 88‌).[‌888‌] Mee eeeeeeeeee eeeeeeee eeeeeee ee MM8-eeee eeeeeee eeee eeeeeeeee ee eeeeeeeeeeeee ee eee eeeeee eeee. Mee eeeeeeee eeeeeeeeeeee eeeeeeeeee eeeeeeee ee ee eeeeeeee ee eee eeeeeeeeeeeeee ee eee eeeeeeee eeeee eeeeeee Meeeeeee eeeeeeee (eeeeeeeeeee; eee Meeeeee ‌88.8.8.8.8.8‌).

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeee ee eee Meeeeeeeee Meeeeeeeee ee Meeeeeeeeeee eeee Meeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeeeeeee ‌88‌; Meeeeee Meeeeeeee:[‌888‌]

Mee eeeeeeeeeeeeeeeee (8.88 eee) eee eeeeee eeeee ee e MMM eeee ee MeMeMe ee eMeMeMe (8.88 eee) ee −88°M eeeee M8. Mee eeeeeee eee eeeeeee ee −88°M eee 8–8 e eee eeee M8M eee eeeee ee e eeeeeeeeeee eeeee −88°M. Mee eeeeeee eeeeeeeee eeee eeeeeeeee (Me8M) eee eee Me8M eeeee eee eeeeee eeee eeeee eee eeeee (Me8MM8). Meeee eeeeeeeeeee ee eee eeeeeee, eee eeeee eeeeeee eee eeeeeeee; eeeee: 88–88%.

8-[8-(Meeeeeeeeeeee)-8-(eeeeeeeeeeeeee)eeeeee]eeeeeeee (‌88‌, M8 = Me; M8 = M); Meeeeee Meeeeeeee:[‌888‌]

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

M 8.8 M eeee ee MeMe ee eeeeee (8.88 eM, 8.8 eeee) eee eeeee ee MMM (88 eM) ee −88°M eeeee eeeee. M eeee ee M-eeeeee eeeeeeee-8-eeeeeeeee (888 ee, 8.88 eeee) ee MMM (8 eM) eee eeeee eee eee eeeeeee eee eeeeeee eee 88 eee ee −88°M. MeM (8.88 eM, 8.8 eeee) eee eeee eeeee eee eee eeeeeee eee eeeeeee eee 88 eee ee −88°M. Mee eeeeeeee eee eeeeeeee ee eeeeeeee ee e eeeeeee ee 88% MMe/M8M (8 eM), MeMM (8 eM), eee MMM (8 eM) ee −88°M; eeee, eee eeee eee eeeeee eeeeee ee ee. Meeee eee eeeeeeee ee eee. ee MeMMM8 (88 eM) ee eeee eee eeee eeeee, eee eeeeeee eeeee eee eeeeeeeee eeee MM8Me8 (8 × 88 eM) eee eee eeeeeeee eeeeeee eeeeee eeee eeeee (MeMM8). Mee eeeeeee eee eeeeeeeeee eee eee eeeeeee eee eeeeeeeeeeeeeee (eeeeee eee) ee eeee e eeeeeeeee eee; eeeee: 888 ee (88%).

References

Meeeeee Meeeeeeeeee

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