Science of Synthesis

Tobrman, T., Science of Synthesis Knowledge Updates, (2024) 1, 151.

Transient 2H-phospholes have been applied only rarely for the preparation of substituted 1H-phospholes. A recent preparation of unsymmetrically substituted 1H-phospholes is based on the reaction of 1-aryl-3,4-dimethyl-1H-phospholes (e.g., ‌66‌), which isomerize to 2H-phospholes (e.g., ‌67‌). Subsequently, the transient 2H-phosphole is deprotonated to give a phospholide ion (e.g., ‌68‌). Then, copper-catalyzed P—C bond formation and repetition of the above reaction sequence completes the synthesis of the pentasubstituted phosphole (e.g., ‌69‌) (‌Scheme 28‌). The developed process allows smooth introduction of aryl and alkenyl substituents.[‌93‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeeeee Meeeeeeeeee 8M-Meeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

M8	Meeee (%)	Mee
8-eeeeeeee	88	[‌88‌]
	88	[‌88‌]

Meeeeeeee, Meee eee ee-eeeeeee eeee eeeeeeeee ee ee eeeeeee eeeeeeee eeeeeeeeeee ee eeeeeee eeeeeeeeeeee[‌88‌] ee eeeeeee e eeeeeeeee ee 8,8′-eeeeeeeeeeee ‌88‌ eee ‌88‌ eee eeeeeeeee 8M-eeeeeeeeee (‌Meeeee 88‌).[‌88‌] Meee ee eeeeeee eeee eee eeeeeeee eeeeeeeee eee eee eeee eeee eee eeeeeeeeee ee 8M-eeeeeeeeee eeee e 8M-eeeeeeeee eee [8,8]-eeeeeeeeeee eeeee eeeeeeee eeeeeeeeeeee eeeee 888 °M. Mee eeeeeee ee eee eeeeeeee eeeeeee ee eee eeeeee eeeeeeee eeeeeeeee; eeeeeeeeeeee, eee eeeeeeee ee eeeeeeeeeee eeee ee eeeeeeee eee e eeeeeeeeeeeeee eeeeeeeee eeeeeeee e 8,8′-eeeeeeeeeee eeee ee ‌88‌, eeeeeee eee eeeeeeeee ee e eeeeeeeee 8,8′-eeeeeeeeeee ‌88‌ ee eeeeeeee eeee eeeeeee eee eeee eeeeeee ee eeeeeeeee ee eee eeeeeeee eeeeeeee.

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeee Meeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeeeee-8,8-ee(8-eeeeeeee)-8-eeeeee-8M-eeeeeeeee (‌88‌, M8 = 8-Meeeeeee); Meeeeee Meeeeeeee:[‌88‌]

8-Meeeeeeeeeeeeee (888 ee, 8.8 eeee) eee e eeee ee 8,8-eeeeeeee-8-eeeeee-8M-eeeeeeeee (‌88‌; 888 ee, 8.8 eeee) ee eeeeee (8.8 eM) eeee eeeee ee e eeeeeee ee MeM (88 ee, 8.88 eeee), 8,8′-ee-eeee-eeeee-8,8′-eeeeeeeee (88 ee, 8.88 eeee), eee M8MM8 (888 ee, 8.8 eeee). Mee eeeeeee eee eeeeeee ee 888 °M eee 88 e eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee eeee eeeeee/MM8Me8 8:8) ee eeee eee eeeeeee ee e eeeee eeeee; eeeee: 888 ee (88%); ee 88–88 °M; 88M MMM (MMMe8, δ): 8.88.

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