Science of Synthesis

Suginome, M.; Ito, Y., Science of Synthesis, (2004) 19, 509.

Isocyanides can be synthesized via α-metalated isocyanides with retention of the isocyano groups (see Section ‌19.7.1.1.9‌). This section deals with the reactions of the α-anions of isocyanides in which the isocyano group participates in the reaction, yielding cyclization products. Detailed reviews covering this method have been published.[‌97‌,‌98‌]

Mee eeeeeeee ee α-eeeeeeeee eeeeeeeeeee eeee eeeeeeeee eee eeeeeee eeeeee 8,8-eeeeeeeeeeeeeee (‌Meeeee 888‌). 8-Meeeeeeeeeeeeeeee ‌888‌, eeeee eee ee ee eeeeeeeeeee eeee eee 8-eeeeeeeee eeeeeeeeeeeeeee ‌888‌, eee eeeeeeee ee ee eeeeeeee ee eeeeeeeeeeeee. Meeeee eeee eeeee ee eeeeeeee eeeee eeeeeeee eeeeeeeeee eeeeeee ee eee eeeeeeeee ee eeeeeeeeeeeeee eeeeeeee, eeeeeee eeeeeeeee eeee eeeeeee eeeeee eeee eeeee e eeeee eeeeeeee eeeeee eeeee ee eee eeeeeeeee ee 8-eeeeeeee eeeeeeee ‌888‌.[‌888‌,‌888‌] Meee eeeeeeeeeee eeeeeee eeeee, eeeeeeeeeeeeee, eeeeeeeeeeeeeeeeee, ee eeeee eeeeee ee eee α-eeeeeeeee, eee eeeeeeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeeeee eee eeeeeeee. Meeee eeeeeeeee eeee eeeee eeee ee eeeeeeeeeeeee (ee MM8Me8), e eeeeeeeee eeeeee ee eeeeee eeeeeee (ee MeMM), ee eeeeeeeee eeeeeeeee (ee MeMM).[‌88‌]

‌Meeeee 888‌ Meeeeeeeeeeeee Meeeeeeee eeeeeee eee Meeeeeee ee α-Meeeeeeee Meeeeeeeeee eeee Meeeeeee Meeeeeeee[‌88‌,‌888‌,‌888‌]

Meee eeee ee eee eeee ee eeeeeeeeeee eeeeeeeeee[‌888‌] eeeeeeee ee eeeeeee eeeeeeeeeee eeeeeee eee eeeeeeeeeeeeee eeeeeee ‌888‌, eeeeeee eeeeeeee eeee ee eeeeeeee ee eeeeeeeee eeeeeeee eeeeeee eee eeeeeee ‌888‌ ee eeeeeee eeeeeeeeeee ee eee eeeee eeeee (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee ee Meeeeeeeeeeeee eee ee Meeeeee ee eee Meeeeeee ee Meeeeeeeeee Meeeeeeeee eeee ee Meeeeeee[‌888‌]

Meeeeeeee ee eee α-eeeeeeeee eeeeeeeeeee eeee eeeeee eeeeee eeeeeeeeeeeeeeee eeeeeeeeeee ‌888‌ eee ‌888‌ (‌Meeeee 888‌). Mee 8-eeeeeeeee eeeeeeeeeeeeeeee ‌888‌ ee eeeeeee ee eee eeeeeeeeeee eee eeeeeeeeeeee eeeeeee ee e eeeeeeee eeeeeeee, eeeeee 8-(α-eeeeeeeeeeee)-8,8-eeeeeeeeeeeeeeeee ‌888‌.[‌888‌] Meeeeeee ee eeeeeeeeeee eeeeeeeeee eeee eeeeee eeeee eeeeeeeeee ee e eeeeeeee eeeeee eeeeeee ee eeee eeeeeeee ee eee eeeeeeeee ee eeeeeeee eeee eeeeeeeeeee eeeeeeeeee.[‌888‌]

‌Meeeee 888‌ Meeeeeeeeeeeeeee Meeeeeeee eeeeeee eee Meeeeeee ee α-Meeeeeeee Meeeeeeeeee eeee Meeeee[‌888‌]

Mee eeeeeeee ee α-eeeeeeeee eeeeeeeeeee eeee eeee eeeeeeeee, eeeeee, ee eeeeee eeeeee eeeeeee eeeeeeeeeee.[‌888‌,‌888‌,‌888‌] Mee eeeeeee, eee eeeeeeee ee 8-eeeeeeeeeeeeee eeeeeeee (‌888‌) eeee eeeeee eeeeeeeeeeeeeee, eeeee ee e eeeeeeeeee eeeeeeeee ee 8-eeeee-8-eeeeeee-8M-8-eeeeeeeeee-8-eee ‌888‌ (‌Meeeee 888‌).[‌888‌] Mee eeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeee ee eeeeeeeeeeeeeee, eeeeeeeee eeeeeeee, e.e. ‌888‌, eeee eeee eee eeeeeeeeeeeee eeeeeeeeeee 8M-8-eeeeeeeeee-8-eeee ‌888‌ ee 88–88% eeeee ee eeeeeeeeee.

‌Meeeee 888‌ Meeeeeeee ee e 8M-8-Meeeeeeeee-8-eee eeeeeee Meeeeeeee ee ee Meeeeee eeee 8-Meeeeeeeeeeeee Meeeeeee eee ee Meeeeeeeee[‌888‌,‌888‌–‌888‌]

8-Meee-8M-eeeeeeee-8-eeeeeeeeee eeeee ‌888‌ eee eeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeee ‌888‌ eeee eeeeee eeeeeeeeeeeeeee (‌Meeeee 888‌).[‌888‌]

‌Meeeee 888‌ Meeeeeeee ee Meeeeeeeeeeeee Meeee eeee ee Meeeeeeeee[‌888‌]

Meeeeeeeee eeeeee ee eeeeeee eeeeeeeeeee ‌888‌ eeee eeeeeeeee eeeeeee eeeeeeee eeeee eeeeeeeeeee eeeeeeeeee (‌Meeeee 888‌).[‌888‌] Mee eeeeee eeeeeeee eee eeeeeeeee eeeee, eeee-eeeeeeee [8+8]-eeeeeeeeeeeee eee eeeeeeeeee β-eeeeeeeeeee ee 8-eeeeeeeeeeeeeee eeee. M eeeeeee ee Meeeeee eeeeeeee eeeeeee eeeeeeee-eeeeeeeeeee eeeeee, eeee ee eeeee, eeeeeeeeeeeeee, eeee, ee eeeee eeeeee, eee ee eeee ee eee eeeeee eeeeeeeee. Meeeeeeee, eeeeee eeeeeee ee eeee ee e eeee ee ee eeeeeeeee eeeeeee eeeeee eeeeeeeeee eeeeeeee eeeeeeeee, eeeeeeee eee eee ee eeeeeeeee eeee-eeeeeeee ee eeeeeeeeeeeeeee ee eeeeeeeee eeeeeeeee ee eeeeeeee eeeee eeeeeee eeeeeee.[‌888‌]

‌Meeeee 888‌ Meeeeee Meeeeeeee eeeeeee eee Meeeeeee ee Meeeeeeeeee Meeeeeeeee eeee Meeeeeeee Meeeeee[‌888‌]

Meeeeee eeeeeeee ee eee eeeeeee eeeeee eeeeeeee α-eeeeeeeeeeeeeeeeeeeee eeeeeeeeeee.[‌888‌–‌888‌]

Meeeeeeeeeee Meeeeeeee

8-Meeee-8-eeeeeee-8M-8-eeeeeeeeee-8-eee (‌888‌); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee 8-eeeeeeeeeeeeee eeeeeeee (‌888‌; 8.88 e, 88 eeee) ee MMM (88 eM) eee eeeee eeeeeeee ee e eeeeeee eeeeeee ee MeM8MMM8MM (8.88 e, 88 eeee) ee 8–88°M, eee eee eeeeeee eee eeeeeee eee 8 e ee ee. Mee eeeeeee eee eeeeeee ee eeeee eee eee eeeeeeeee eeeeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeee eee eeeeee eeee M8M, 8% MMe, eee 88% MeMMM8 eeee, eeeee (MeMM8), eee eeeeeeeeee ee eeeee. Mee eeeee eeeeeee eee eeeeeeee ee e eeeeeee eee (8.8 e). Meeeee eeeeeeeeee ee eee eeeee eeeeeee eeeeeeee eee eeeeeee; eeeee: 8.88 e (88%).

Meeeeeee ‌888‌ ee eee Meeeeeee ee Meeeeeeeeee Meeeeeeeee eeee α,β-Meeeeeeeeee Meeeeee ee Meeeeeee; Meeeeee Meeeeeeee:[‌888‌]

M eeee ee MeeMMM (8 eeee) eee ee α,β-eeeeeeeeeee eeeeee (ee eeeeeee) (8 eeee) ee MMMM/Me8M (8:8) eee eeeee eeeeeeee ee e eeeeeee eeeeeeeeee ee MeM (ee. 8.8 eeeee) ee Me8M. Mee eeeeeee, eeeee eeeeeee ee eeeeee, eee eeeeeee eeee M8M eeeee 88 eee eee eeeeeeeee eeee Me8M. Mee eeeeeeee eeee eeeeeeee ee eeeeeeeeeeeeeeeee, eeeeeeeeeee, ee eeeeeeeeeeeeee.

References