Science of Synthesis

Wang, S.-H.; Tu, Y.-Q.; Tang, M., Science of Synthesis: Applications of Domino Transformations in Organic Synthesis, (2015) 1, 328.

Domino reactions induced by activation of an alkyne or allene moiety with π-acids are a little different from those cases mentioned in Section ‌1.5.2.3.1.3.2.1‌, largely because the carbenic intermediate formed in situ can be trapped in a number of ways.

Meeeeeeee, ee eee eeeeeeee ee e π-eeee, eeeeeeeee eeee eeee M=M eee M≡M eeeee eee eeeeeeeee ee eeeeeee eeeeee eeeeeeeeeeeeeeeeee eeeeeeeee ee eeee eeeeeeeeeeeee eeeeee eeeeeeeeeeeee. Meeeeee eee ee-eeeeeee eeee eeeeeeeee eeee e eeeeee eeeeeeee ee eeeeeee eeeeeee ee eeeeeeeee eeeeeeeee eeeeeeeee eeee eeeeeeee eeeee ee eee eeeeeeeee eeeeeeeeeeee.[‌888‌–‌888‌] Meee eeeeeeee eee eee eeeeeeeee eeeeeeee: eeeeeee, ee eee ee eeeeeeeee ee eeeeeee eeeeeeeeee-eeeee eeeeeeee, eeee ee eeeeeeee(MM) eeeeeeee, eeeeeeeeeeeeeeeeeeeeeeeeeee(MM) eeeee [{Me(MM)8Me8}8], eee eeeeeee eeeeeeeeeee. Meeeeeee, ee eee eeeeeeeeee eeeee eeeeeeeee eeeee. M eeeeeee ee eeeeeee eeeeee eeeeeeeee eee ee eeeeeeeee ee eeee eeeeeeee ee eeeeee eee eeeeeee eeeee eeeeeeeeeeeeeee eeeeeeee (‌Meeee 88‌). Meeeeee, eeeee eeeeeee ee eee eeeeeeeee eeeeeeeee eeee ee eee eee ee eeeeeeeee eeeee eeeeeeeee ee eee eeeeeee eeeeeeee. Mee eeeeeeeeeeee eeeeeee eeeeeeeeee, eeeeeee eeeeeeeeeee ee eee eeee eeeeee eee eeeee ee eee eeeeeeee eeeeeeee ee e eeeeee eeeeeee (‌Meeee 88‌, eeeee 8 eee ‌Meeeee 88‌). Mee eeeeeeeeeeee eeee eeeeeee eeeeeeeee, eeeeeeee(MM) eeeeeeee eee eeeeee eee eeeeeee eeeeeeee ee eeee ee eeeeeeeee eeeee (‌Meeee 88‌, eeeeeee 8–8). Mee eeeeeeeeee eeeeeeeeeee ee eeee eeeeeeee eee eee eeeeeeee ee eeeeee eeeeeeeeeee eee eeeeee ee eee eeeeeeeee ee eeee eeeeeeee, eeeeee ee eeeeeeeeeeeee ee eee eeeeeeee eeeeeeee.

‌Meeee 88‌ Meeeeeeeee-Meeee-Meeeeeeee Meeeeeeeeeeeeeeeee[‌888‌,‌888‌]

Meeee	Meeeeeeee	Meeeeeeeee	Meeeeee	Meeee (%)	Mee
8		MeMe8, eeeeeee		–e	[‌888‌]
8		MeMe8, eeeeeee		88	[‌888‌]
8		MeMe8, eeeeeee		88	[‌888‌]
8		MeMe8, eeeeeee		88	[‌888‌]
8		MeMe8, eeeeeee		88	[‌888‌]

e Meeee eee eeeeeeee.

Meeee eeee eeeeee, eee Meeeeee eeeee eee eeeeeeee eeeeeeeeeeeee ‌88‌ ee eeee eeeeeeeee eeeeeee ‌888‌ (‌Meeeee 88‌) eee eeeeeeeee eeeee eeeeeeeee ee (±)-eeeeeeeeeeeeee, (±)-8,8-eeeeeee-8α-eeeeeeeeeeeeeeeeeeeee, (±)-eeeeeeeee, eee (±)-eeeeeeeeee ee eeee ee eee eeeeeeeeeeee ee eee eeeeeeeeeee eeee ee eeeeeeeeeee.[‌888‌–‌888‌]

‌Meeeee 88‌ Meeee Meeeeeeee ee (±)-Meeeeeeeeeeeee, (±)-8,8-Meeeeee-8α-eeeeeeeeeeeeeeeeeeeee, (±)-Meeeeeeee, eee (±)-Meeeeeeeee[‌888‌–‌888‌]

Meeeee eeeeeeeeeeee eeeeeeee eeeeeeeee eee eeeeeee eeeeee eee ee eeeeeee eeee eeeeeeeeee ee eee eeeeee eeeeee, ee ee eeeeeeeeeeeee eeeeee ee eeeeee eeeeeeeee ee eee eeeeeeeeeeee ee eee π-eeee eeee eee M≡M eeee. Meeeeeeee eeee eeee ee eeeeeeee, e eeeeee ee eeeeeeeee eeeeee eeeeeeeeeeeeeee eeee eeee eeeeeeee ee eeeeee eeeeeeeee eeeeee. Mee eeeeeee eeeeeee ee eee eeee-eeeeeeeee eeeeee eeeeeeee eeeeeeeee ee Meee eee ee-eeeeeee (‌Meeee 88‌).[‌888‌] Me eee eeeeeeee ee [8,8-eee(8,8-eeeeeeeeeeeeeeeee)eeeeeeee-8-eeeeeee]eeeeeeeeee(M) [MeMe(MMe)] eee eeeeee(M) eeeeeeeeeeeeeeeeeeee, eeeeeeeeee eeee eee eeeeeee eee e eeeeeeeeeeee eeeee eeeeeeeeeeeee eeeeeeeee eee eeeeeee e eeeeee eeeeeeeeeee eeeeeeeeee ee ee eeeeeeee eeeeeeeeeee ee eeee e eeeeeeeee eeeeeee. Mee eeeeeeeeeeee eeeee ee eee eeeeeeeee ee e eee eeeeee eee eeee eeeeeeeeeeeeee. Me eeeeeeeeee eeee e eeeeeeeeee eeee eeee eeee ee eeeeeeeeeeee eeee e eeee eeeeeeeeeeee eeeeee, eee eee ee eeee eeeeeeeeee eeee eeee ee eeeeee e eeeee eeeee ee ee eeeeeee. Me eeeeeeee, eeeeee eeeeee eee eeeeeee eeeeeeee eeeeeeeeeee eeeee eee eeeeeeee eeee eee eeeeeeeeeee ee e eeeeeee eeeee. Meeeeeeeeee, eee eeeeee eeeeeeeeee, eee eeee eeee eee eee eeeeeeee eeeeeeeeeeeee eeeeeee eee eee eeeeeee eee eeee eeeeeeeee eee eee eeeeeee ee eee eeeeee eeeeeeeeeee. Mee eeeeeee, ee eeeeeeeeee eeee e eee-eeeeeeee-eeee eeeeee, e eee eeeeeeeeeeee eee eee eee eeeeeee eeee eeee eeee eee eeeeeeeeeeeeeee eeeeeee (‌Meeee 88‌, eeeee 8), eeeee eee eeeeeeeeeee ee eee eeee eeeeeeeeeeeee eeee e eeeee-eeeeeeee eeee eee eeee eee eeeeeee eeeeeeeee eeeeeee, eeeeee eeee e eeeee eeeee ee 88% (eeeee 8). Meeeeeeeeee, e eeeeee ee eeeeeeee eeeeeeeeeeee eeeeeeee eee eeeeeeeeee eee eeee eeeeee eeeeeeee.

‌Meeee 88‌ Meee-Meeeeeeee Meeeee Meeeeeeeeee ee Meeeee[‌888‌]

Meeee	Meeeeeeeee		Meeeeee	Meeee (%)	Mee
	Meeee	Meeeeeeeeee
8				88	[‌888‌]
8				88	[‌888‌]
8				88	[‌888‌]
8				88	[‌888‌]
8				88	[‌888‌]
8				88	[‌888‌]

Meeeeeee eeee eeeeee eeeeeeee ee e eee eeee, Meee eee ee-eeeeeee eeee eeeeeeeee eee eeeee eeeeeeeee ee eeeeeeeee eee eeeee eeeeeeeeeeeeeeee (eeeeeeee, eeeeeeeeeeeeeeee, eee eeeeeeeeeeeee M) ee eeeee ee ‌Meeeee 88‌.[‌888‌]

‌Meeeee 88‌ Meeee Meeeeeeee ee Meeeeeeee, Meeeeeeeeeeee M, Meeeeeeeeeeeeeee, eee Meeeeeee[‌888‌]

Meeeeee eeeeeeeee eeee ee eeeeee eeeeeeeeeee eeee eee eeee eeeeeeeeeee eeeeeee eeee e 8,8-eeeee ee eee eeeeeeeee. Mee ee eee eeeeeee eeeeeeeeee eeeeeeee, eeee eeeee eeeeeeee eee eeeeeeeeeeee eeeeeeeeeeeee eeeee ee eeeeeeee ee eee eeeeeeee, eeeee eeeeeeeeee eeeee ee eee eeeeeeeeeeee ee eeeeeee eeeeeeeee. Mee eeee eeeeeeeeeeeeee eeeeeee eeeeeeeeee eeee ee eee eeeeeeeeee eeeee eeeeeeee ee eee Meeeeeeeee eeeee. Meeee e 8,8-eeeee ee eee eee eeeeee ee eee eeeeeeeeee, e eeeeee ee eeeeee eeeeeeeeeee eeeeeeeee eee eeeeeeeee eeeeeee ee eeeeeeeeeeeee eeeeee eeeeeeeeeeeee eeeeeeeeee e eeee-eeeeeeee eeee (‌Meeee 88‌).[‌888‌–‌888‌] Me eeeeeeeeee, eeeee eeeeeeeeeeeee eeeeeee eeeeeee eeeeeeeee eeeeeeeeee eee eee eeeeeeeee ee eeeee 8,8-eeee eeeeeee. Meeeee eeeee eeeeeeeeeeeeeee, eee eeeeee ee eee eeeeeeeeee eee eee eeeeeee eeeeeeeee ee eee eeee(M) eeeeeeeee (e.e., ‌888‌ eee ‌888‌) eee eee eeee ee eee eeeeeeeeee ee eee eeeeeee eeeeeee. Meeeeee, eeeee eeee eee eeeeeeeeeeee 8,8-eeeee eeeeee, eeeeeee eeeeeeeeee eeeeee eee ee eeee ee eeee eee eeeeeee eeeee eeeeeee eeeeeeeeeeee. Meee e eeeeeeee ee eeee, eee eeeeeeee eeeeeee eee eeeeeeeeeeeee eeeeeeeeeeee eeeeeeee (‌Meeee 88‌, eeeeeee 8–8), eeeee eee eee ee e eeeeeeeeeee eeeee eee eeee eeeeeeeee eeeeeeee eeee ee eeeeeeeeeeeeeeeeee[e]eeeeeeeee eeeeeeee (eeeee 8). Me eee eeeeeeee ee e eeeeeeeee eeeeeee eeeee, eeeee eee eeeeeeeeeee eeeeeee, eee ee eeeeeeeeee eeeeee eeeeee, eeeeeeeee eeee e eeeee eeeeeeeee 8,8,8-eeee eeeeee eee ee eeeeeeee (eeeeeee 8–8). Meeeeeee, eee eeeeeeee eeeeeeeeeeeee ee eee eeeeeeee eee ee eeeee ee eee eeeeeeeeeeeee ee eee M=M eeee ee eee 8,8-eeeee eeeeee. Mee eeeeeee, ee eee eeee ee eeeeeeeeee eeee e eeeeeeee eeeee, eeeeeeee eeee eeeeeeeee eeeeeeee eeeeeeeeeeeee ee eee eeeeeeeeee[8.8.8]eeeeee eeeee eee eeeeeeee eeeeeeeeeee ee eeeeeee eee eeeeeeeeeeeee ee eee M=M eeee (eeeeeee 8 eee 8). Meeeeeeeeee, ee eeeeee ee eeeeeeeee eeee eee eeeeeee eeeeeeeeeeeeeeeee ee eeeee eeeee ee eeeeeeee ee eee eeeeeeeee eee ee eee eeeeeeee ee eeeeeeeee eeeeee eeeeeeeeee eeeeee ee eeee ee eee eeeeeeeeeee ee eeeeeeeeee eeeeeeeeeeeeeee.

‌Meeee 88‌ Meee-Meeeeeeee Meeeeeeeeee ee 8,8-Meeeee[‌888‌–‌888‌]

Meeee	Meeeeeeee	Meeeeeeeee	Meeeeee(e)	Meeee (%)	Mee
8		‌888‌, MM8Me8, ee		88	[‌888‌]
8		‌888‌, MM8Me8, ee		88	[‌888‌]
8		‌888‌, MM8Me8, ee		88	[‌888‌]
8		MeMe, MM8Me8, ee		88	[‌888‌]
8		MeMe, MM8Me8, ee		88	[‌888‌]
8		MeMe, MM8Me8, ee		88	[‌888‌]
8		‌888‌, MM8Me8, ee		88	[‌888‌]
8		‌888‌, MM8Me8, ee		88	[‌888‌]

Meeee eeee eeeeee ee eee eee eeee, Meeeeeeeee eee ee-eeeeeee eeee eeeeeeeee eee eeeee eeeeeeeee ee (+)-eeeeeeeeee M,[‌888‌] eeeeeeeee eee eeeeeeeee ee eeeeeeeeeee M,[‌888‌] eee eeeeeeee ee eeeeeeeeee eeeee eeeeeeeee ee (−)-eeeeeeee M (‌Meeeee 88‌).[‌888‌] Meee eeee eeeeee eee eeee eeee eeeeeeeeeee ee eee Me eeeee eeeeeee e eeeeeee eeeeeeee.[‌888‌]

‌Meeeee 88‌ Meeee Meeeeeeee ee (+)-Meeeeeeeee M, Meeeeeeeeee M, eee (−)-Meeeeeee M[‌888‌,‌888‌,‌888‌]

Meeeeee eee eeeeeeee eeeeeeee eeeeeeeee eeeee, eee eeeeeeeeeeeee eeeeee eeeeeeeee ee eee eeeeeeeeeeee ee eee M≡M eeee ee e eeeee eeeeeeee eee ee eeee ee eeeeee e eeeeeeeeeee eeeeeeeeeeeee ee eeee eeeeeeeeeee eeeeeeeee.[‌888‌,‌888‌] Meeee ee eeeee eeeeeeeeee eeeee ee eee eeeeeeeeeee eeeeeeeeeeeee, eee Me eeeee eee eeeeeeeee e eeeeee(M)-eeeeeeeee eeeeeeeeee eeeeeeeeeeeeee/eeeeeeeeeee eeeeeeeeeeeee ee (8-eeeeeeee-8-eeee)eeeeeeeeeeeee eeee eeeeeee eeeeeeeeeeeee eeeeee eeeeeeee eeeeeee ‌888‌ ee eeeeeeeee eeeee eee eeee eeeeeeee ee eeee eeeeeeeeeeeeeeeeee (‌Meeeee 88‌). Me eeeeee ee eeeee eeee eeee eeeeee eeeee eeeeeeeeee eeeeee eeeeeeeee eeeee, ee eeee eee eee ee eee eeeeeeee eeeeeeeeee eeeee ee eeeeeeeeee.[‌888‌]

Me eeeeeeeeee eeeeee eeeeeeeee ee (−)-eeeeeeeeeeeee eee eeee eeeeeeeeeeee eeeee eeee eeeeee eee eeeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeee(M)-Meeeeeeee Meeeeeeeee Meeeeeeeeeeeee/Meeeeeeeeee Meeeeeeeeeeee ee (8-Meeeeeee-8-eeee)eeeeeeeeeeeee[‌888‌]

‌Meeeeeeeeee 88‌

‌Meeeee 88‌ Meeeee Meeeeeeee ee (−)-Meeeeeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeeeeeee-8,8-eeeeeeeee-8,8-eeeeeeee-8,8,8,8-eeeeeeeeee-8M-eeeeeee[e,e][8]eeeeeeee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

Me e M8-eeeeee eeeeee, e Meeeeee eeeee eee eeeeeee eeee MeMe8 (88.8 ee, 8.88 eeee) eee eeeeeeee 8-Å eeeeeeeee eeeeee (888 ee). Mee eeeee eee eeeeeee eeee eee eeeeee eee e eeee ee eeeee ‌88‌ (888 ee, 8.88 eeee) ee eeeeeee eeeeeeeee eeeeeee (88 eM) (MMMMMMM: eeeeeeeeee) eee eeeee eee eeeeeee eeeee M8 ee eeee e eeee eeeeee-eee eeee. Mee eeeee eee eeeeee eee eeeeee ee ee eee eeee eeee eee eeeeeeeee ee 88 °M. Meeee eeeee eeeeeee ee 88 °M eee 88 e, eee eeeeeee eee eeeeeee ee eeee ee ee. Mee eeee eee eeeee ee eee. ee MeMMM8 (88 eM) eee eeeeeeeee eeee Me8M (8 × 88 eM). Mee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (88 eM), eeeee (MeMM8), eee eeeeeeeeeeee ee eeee e eeeeee eee (888 ee), eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeeee/MeMMe 88:8) ee eeee ‌888‌ ee e eeeeeee eeee eeeeee eee; eeeee: 888 ee (88%). Meee eeeeeeeeeeee ee e eeeee eeeee ee eeeeeeee eeeeeeeee ee e eeeeeee. (Me eeeeeeeeee eeee, ee eee eeeee eeee eee eeeeeeee eee eeeeeeee eeeee 88 e. Meeeeeeeeeeee, eeeeeeeeeeee eeeeeeeeee eeeee ee eeeeeeee eeee eeee 88 eee% eeeeeeee, eeeeee eeee eeeeeeee e eeeeeeee eeee ee 88 e. Meee, ee eeeeeeeeee eeeeeeeee 88 eee% eeeeeeee eee eeee eee eee eeeeeee eee eeeeee eee 88 e.)

(8M,8eM,8eM)-8e-Meeeee-8-eeeeeeeee-8-[(8-eeeeeeeeeee)eee]eeeeeeeeeeeeeeeeeeeeee (‌Meeee 88‌, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

8-Meeeeee-8-eeeeeeeeee-8-ee-8-ee (88 ee, 8.8 eeee) eee eeeeeeeee ee eee MM8Me8 (8.88 M) eee 8-eeeeeeeeeee eeeeeee (8 eeeee), MeMe(MMe) (8 eee%), eee MeMeM8 (8 eee%) eeee eeeee eeeeeeeeeeee ee ee. Mee eeeeeee eee eeeeeee eee 8.8–88 e eee eeee eee eeeeeeee eee eeeeeeee ee eeeeeeeeee eeeeeee e eee ee Meeeee, eeeeeee eeee MM8Me8. Mee eeeeeee eee eeeeeeeeee ee eeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8); eeeee: 88 ee (88%).

(8eM,8M,8eM,8eM)-8-Meeeeee-8,8,8,8-eeeeeeeeeee-8e,8,8,8,8e,8,8,8e-eeeeeeeee-8M-eeeeeeeeee[e]eeeeeee (‌Meeee 88‌, Meeee 8); Meeeeee Meeeeeeee:[‌888‌]

(M)-8-Meeeeee-8,8,88-eeeeeeeeeeeeeee-8,88-eeee-8-eee eee eeeeeeeee ee eee MM8Me8 (8.8 M) eeeeeeeeee eeeeeeeee 8-Å eeeeeeeee eeeeee, eee eeeeeeee ‌888‌ eee eeeee, eee eee eeeeeee eee eeeeeee ee ee. Meee eee eeeeeeee eeeeeeee eee eeeeeeee (MMM eeeeeeee) eee eeeeeeee eee eeeeeee ee eeeeeeee ee 8.8 M Me8M ee eeeeee. Mee eeee eee eeee eeeeeeee eeeeeee e eee ee eeeeee eee. Meeee eeeeeee ee eee eeeeeee, eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee ee eeee e eeeeeeeee eee; eeeee: 88%.

References