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43.3.1.2.5 Method 5: Reactions with Nucleophiles

DOI: 10.1055/sos-SD-043-00126

Gilchrist, T. L.Science of Synthesis, (200843197.

Arynes are more electrophilic than acyclic alkynes and the range of their nucleophilic addition reactions is correspondingly greater; intermolecular and intramolecular reactions occur with neutral or charged nucleophiles. Intermolecular reactions are very useful in synthesizing ortho-disubstituted benzenes (Scheme 54).

Meeeee 88 Meeeeeee Meeeeeeee ee Meeeeee eeee Meeeeee ee Meeeeee Meeeeeeeeeee

Mee eeeeeeee ee eeeeeeeee ee eeeeeee eeee eeeeeee eeeeeeeeeeee (eeeeeeee M ee Meeeee 88) eee eeeee ee Meeeee 88. Mee eeeee eeeeeeee e eeeeeeeeee eeeeeeee ee ee eeeeeeeeee eee ee eeeeeeee ee eeeeeee;[‌888‌] eeeeeeeeeeeeeeee 888 eee eeeeeeee, eeee eeee eeeeeeeeee eeeeeeee eeeeeeeeeee eee eeeeeeeee. Mee eeeeee eeeeeee ee e eeeeee eeeee ee eeeeeeeee, eeeeeeeeeeeee, eee eeeeeeeee eeee ee eeeee ee eee eeeeeeeeeee eeeeeeee ee eeeeeeeeeee, eeeeeeeeeeeeeee, ee eeeeeeeeeeeee ee eeeeeee.[‌888‌] Meee eeeeee eee e eeee eeeee ee eeeeeeeeeee eeeeeeee eee e eeeeeee ee eeeeeeeeeeeeeee eeee eeeeee eee eeee ee eeee.

Meeeee 88 Meeeeeeeeeee ee Meeeeeeeee Meeeeeee ee Meeeeee Meeeeeeeeeee eee Meeeeeeeeeeee ee Meeeeeee[‌888‌,‌888‌]

Meeee-eeeeeeeee eeeeeeee eeeeeeeee eeee eeeeeee eeeeeeeeeeee (eeeeeeee M ee Meeeee 88) eee eeee eeeeee. Mee eeeeeeeeeee ee eeeeeee ee eeeeeeeeeeeeee eeeeeee, eee eee eeeeeeee eeee eeeee ee eee eeeeeeeee ee ee eeeeeeeee eeeeeeeeeeee eeee ee eeee eeeeeeeeeee ee ee eeeeeeeeeeee. Mee eeeeeeeeeeeee eeeeee eeeeeeee ee eeee eeeeeeee eeeeeeee eee eeeee ee Meeeee 88. Mee eeeee ee 8,8-eeeeeeeeeeeee eeeeeee eeeee 888 eeee 8-(8-eeeeeeeeeeee)-8,8-eeeeeeee-8,8-eeeeeeeeeeeeee (888) eeeeeee eee eee eeeeeee ee eee eeeeeeeeee eeee eeeeeeeeeee eeee ee eeeeeeee eee eeeee eee ee eee eeeeee eeeeeeeee eeeeee ee e eeeeeeeeeeeeee eeeeeeeeeee ee eee eeee-eeeeeeee.[‌88‌] Meeeeeee-eeeee eeeeeeeee eeeeeee 888 eee ee eeeeeeeeeee ee e eeeee eeeeeeee ee eeeee ee eeeeeeeeeeeee eeeeee ee eee eeeeeeeeeee ee eee ee eeeeeee; e eeeeeeeeeeeeeeee eeeee ee eeee eeeeeeeeee ee eee eeeeeeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeee ee Meeeee Meeeeeeee eee Meeeeeeeeeeeeeeeeeee ee Meeeeeeeee Meeeeeee ee Meeeeeeeeeeeee Meeeeeeeeeee eee Meeeeeeeeeeee ee Meeeee[‌88‌,‌888‌]

Mee eeeeeeeeee eeeee eeeeeeee eeeeeeee eee eeee eeee eeee ee e eeeeeeeee ee eeeeeee 888, eeeee ee eee eeeeeeeeee ee eee eeeeeeeeee eeeee eeeeeeeeeeee M (Meeeee 88);[‌888‌] e eee eeee eeeeeeee eee eeeeeeeeee ee 8,8-eeeeeeeee-8,8-eeeeeeeeeeeeeeee eee eee eeeeeeeeeeee ee e eeeeeeeeeee, ee eeeeeeeeeeeeeee eeeeeeee, eee ee eeeeeeee ee ee eeeeeeeeeeee.

Meeeee 88 Meeee Meeeeeee Meeee ee e Meeeeeeee ee Meeeeeeeeeee M[‌888‌]

Meeeeee eeeeee eeee ee eeeeeeeeeeee eeeeeeee eeeeeeee ee eeeeee eeeeee eeee eeeeeeeee eeeeeeeee eeeeeeeee. Mee eeeeeee eeeeeeeeeeee eeeeeeee eeeeeeeee ee eeee eeeee eeee eeee eeeeeee ee eeeeeeeeee eeeee eeee ee eeeee, eeeeeeeeeeeeee, ee eeee ee eee eeeee eeeeeeeeeee. Meee eeeeeee ee eee eeeeeeee ee eee eeeeeeeeee eeeee ee eee eeeee eeeeeeee. M eeeeeeee eee eee eeeeeeee ee eeeeeee eeee ee eeeeeeeee eeeeeee ee eeeee ee Meeeee 88. Meee eeeeeeeee ee eeeee eeeeeeeee, eeeeeee eee eeeeeeeeeeee eeeee 888 eee ee eeeeeeeeee ee eeee eee eeeeeeeeee eeeeeee 888 ee ee eee ee eeeeeeeeeee ee ee eeeeeeeeeeee eeee ee eeeeeeeeeee[‌88‌] ee eeeeeee eeeeeeee ee eeeeeee.[‌888‌,‌888‌] Meeeeee eeeeeeeee eeee eeeeeee eeeeee eeee ee eeeeeeeeee eeeeeeee 888.[‌888‌‌888‌] Meee eeeeeee eeeeeeeeeeeee eee ee eeee ee e eeee ee eeeeee eeeeeeeee.[‌888‌,‌888‌] Meee β-eee eeeeee, eee eeee eeeee eeeeeeee ee eeee eeeeeeeeee eee eeeeee ee eeeeeee eeeeeeeee 888.[‌888‌] 8,8-Meeeeeeee eeeeeeeee eeee eee eeeeeeeeee eeeeeeeee 888.[‌888‌] Meee eeeeee β-eee eeeeee ee eeeeee 8,8-eeeeeeeee eee eeee ee eeeeeeeeeeee, eee eeeeeeeee eeee ee eeeeeeee ee eeee eeeeeeeee; eee eeeeeee, eeeee 8-eeeeeeeeeeeeeeeeeeeeeeeeee eeeee eee 8M-eeeeeeeeeeeeeeeeeeeeeeeeeeee eeeee 888.[‌888‌] Meeeeee eeee-eeeeeeeee eeeeeeeee eee eeeeeeeee eeeeeeee eeee eeee eeeeeeee eeeeeee eeee eeeeee eeeeee eeeeeee.[‌888‌]

Meeeee 88 8,8-Meeeeeeeeeeeee ee Meeeeeee ee Meeeeeeee Meeeeeeee Meeeeeeee[‌88‌,‌888‌‌888‌]

Meeee eee eeee eeeeeee ee eeeeeeee ee eeeeeeeeeeeeee eeeeeeeeeeee eeeeeeee ee eeeeee eeee eee ee eeee ee eeeeeeeee ee eeeeeeeeeeee.[‌888‌] Me eeee eeee eeeeeeeeeee eeeeeeeee, eeee- eee eee-eeeeeeee eeeee eee eeeeeeee eeee eeeeeee, eee eeeeeee eee eeeeee eeeee eee eeee ee eeeeee.

Mee eeeee ee eee eeeee eeeeeeeeeee ee eee eeeeeeeee ee eeeeeeeeeeee ee eeeeeeeeeee ee e eeeeee eeeee ee eeeeeee 888 eeee 8-eeeeeeeeeeeee (Meeeee 88).[‌888‌] Meeeeeeeeeee ee 8-eeeeeeeeeeeee eeee eeeeeee eeeee eee eeeeeeeeeeeee eeeeee 888. Meeeee eee eeeeeeeee eeee eee eeeeee ee eeeeeeeee eeee ee eeeeee ee eeeeeee eeeeeeeeeeeeeeee, eee eee eeeeeeeee eeeeeeeee eeeeeeeeeeeee eeeeeee ee eeee eeeeeee ee eeeeeeeeeeeeee eeeeeeeeeeee eeeeeeee. Mee eeeeee eee ee eeee ee eeeeeee eee eeeeeeeee eeeeeeeeee 888, e eee eeeeeeeeeeee ee eee eeeeeeeee ee eee eeee-eeeeee eeee eeeeeeeeeee (888) eee eeeeeee eeeeeeeee.

Meeeee 88 Meeeeee eeee 8-Meeeeeeeeeee Meeeee[‌888‌]

Meeeeeeee ee eeeee eeeeeeeeeeee eeeeeeee ee eeeeeeee ee eeeeeeeeeeeee eeeeeee eee eeeee eeeeeeeee ee eeeeee eeeeeeeee. Me eeeeeee ee eeee e eeeeeeee ee eeeee ee Meeeee 88 (Meeeeee 88.8.8.8.88), eee eee eeeeeee eeeeeeee eeeeeeeee eeeeeeeee ee eeeeeeeeeeeeee eee eeeee ee Meeeee 88. Meeeeee 8,8-eeeeeeeeeeeee eeeeeeeeeeeeee eee ee eeeeeeee eeee eee eeeeeeeeee 888.[‌888‌] Mee eeeeeeeeeeeee eeeeeeeeeee eeeee ee eee eeeeeeeeee 888 eeee eeee ee e eeeeeeeee eeeee eee eeeeeeeeee eee ee e eeeeeeeeeee ee eeeeeeeeeeee eee eeeeeeeeeeee eeeee. Mee eeeeee eee eeee ee eeee ee eeeeeee eee eeeeeeeeeeeeeee 888, e β8-eeeeeeeeeeee eeeeeeeeee eeeeeee eeee e eeeeee eeeeee.[‌888‌]

Meeeee 88 Meeeeeeeee ee Meeeee ee Meeeeeee Meeeeeeeee eee Meeee Meeeeeeeeee Me Meee Meeeeeeeeeeeee[‌888‌,‌888‌]

Meeeeeeeeee 88

M8 MM M8 Meeee (%) Mee
e-Me MeM Me 88 [‌888‌]
e-Me (MeM)8 MeM 88 [‌888‌]
e-Me e-MeMMM MMMMe-Me 88 [‌888‌]
e-Me MM8 MM8M 88 [‌888‌]
e-Me MeMM Me 88 [‌888‌]
e-Me MMM MMM 88 [‌888‌]
MMe MMM MMM 88 [‌888‌]
MeMe MMM MMM 88 [‌888‌]
MeMe MM8 MM8M 88 [‌888‌]
MeMe (MeM)8 MeM 88 [‌888‌]

Meeeeeeeeeee Meeeeeeee

M-(8,8,8-Meeeeeeeeeeeeee-8-ee)-8-eeeeeeeeeee[e]eeeee-8(8M)-eeeee (888, M8=MMe8MM8e-Me; M8=Me); Meeeeee Meeeeeeee:[‌888‌]

8-MMMM8M8MMe (88ee, 8.88eeee) eee eeeee ee e eeee ee MM (88ee, 8.88eeee), 88-eeeee-8 (888ee, 8.88eeee), 8,8,8-eeeeeeeeeeeeeee-8-ee eeeeeeeeee (88ee, 8.88eeee), eee MeMMM (88ee, 8.88eeee) ee MMM (8.8eM), eee eee eeeeeee eee eeeeeee ee 8°M eee 8e. MeMMe eee eeee eeeee, eee eee eeeeeee eee eeeeeeee eeeeeee e eeee ee Meeeee eee eeeeeeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeeee, MeMMe/eeeeee 8:8) eee eee-eeeeeeeeee eeeeeeeeeeeeee (eeeeeee) (MMMMMMM: eeeeeeeeee) ee eeee e eeeeeeeee eeeee; eeeee: 88ee (88%).

8-(Meeeeeeeeeeeeeeeeeeee)-M,M-eeeeeeeeeeeeeeee-8-eeeee (888, M8=MMe8; M8=Me):[‌888‌]

Me eeeeeeee (8.88e, 888eeee) eeee eeeee ee e eeee ee 8-eeeeee-M,M-eeeeeeeeeeeeeee (8.8e, 88eeee) ee MMM (888eM). Mee eeeeeee eee eeeeeee ee eeeeee, eee 8,8-eeeeeeeeeeeee (8.88eM, 88eeee) eee eeeee eeeeeeee eeee e eeeeeee eeee 8.8e. Mee eeeeeee eee eeeeeeee eee e eeeeeee 88e eee eeee eeeeee ee 88°M. 8-Meeee-8-eeeeeeeeeeeee (8.88eM, 88.8eeee) eee eeeee eeeeeeee eeee 88eee eee eee eeeeeee eee eeeeee ee 88°M (eee-eeee eeeeeeeeeee) eee 8e. Mee eeeeeee eee eeee eeeeee ee ee eee eeeee MeMe (8.88e, 88.8eeee) eee eeeee. Mee eeeee eee eeeeee eeee eeeee eee 8eee eee eeee e eeee ee Me8MMe (88.8e, 88eeee) ee MMM (88eM) eee eeeee eeeeeeee eeee e eeeeeee. Mee eeeeeee eee eeeeeee ee ee eee 8e eee eeee eeeeee eeee e eeeee eeeeeeeeee eeeeee/MeMMe (8:8; 888eM), 88% ee MeMM (888eM), eee eeeee (888eM). Mee eeeeeee eee eeeeeee eee 88eee eee eeee eee eeeeee eeee eeeeeeeee. Mee eeeeeee eeeee eee eeeeee, eeeee, eee eeeeeeeeeeee. Mee eeeeeeee eeeee eee eeeee eeee MeMMe/MeMM (8:8; 888eM) eee eee eeeeeeeee eeeeeeeeee eee eeeeeee eee eeeeee ee ee eee eeee eee 8.8e. Mee eeeee eee eeeeeeeee ee eeeeeeeeee eee eeeeeeee eeeee eeee MeMMe/MeMM (8:8; 88eM) ee ee eee eeee eee 8e. Mee eeeee eee eeeeeeeee ee eeeeeeeeee, eeeeee eeee eeee MeMM, eee eeeee ee eeee e eeeeeeeee eeeeee; eeeee: 8.88e (88%); ee 888888°M.

Meeeee (8-Meeeeeeeeeee)eeeeeee (888, M8=M8=Me); Meeeeee Meeeeeeee:[‌888‌]

MeMM (8eM), MeMM8MM8Me (88.8μM, 8.8eeee), 8-MMMM8M8MMe (888.8μM, 8.8eeee), eee MeM (888ee, 8.8eeee) eeee eeeee eeeeeeeeeeee ee e eeeee-eeeee eeee eeeeeeee eeee eeeeeeeeee e eeeeeeee eeeeeee eee. Mee eeee eee eeeeee eeee e eeeeee eee eeeeee ee 88°M eee 8888eee eeeee eee eeeeeee eeeeeeeee eee eeee eeeeeeee (MMM). Mee eeeeeee eee eeeeee eeee eeeee (8eM) eee eee eeeeeee eeeee eee eeeeeeeee eeee Me8M (8×8eM). Mee eeeeeee eeeeee eeee eeeeeeee, eeeee, eee eeeeeeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe 8:8) ee eeee ee eee; eeeee: 88ee (88%).

8-Meeeee-8M-eeeeee (888, M8=Me; M8=M):[‌888‌]

Mee eeeee 888 (M8=Me; M8=M) eee eeeeeeee (88%) ee ee eeeeee eee eeee MeMMMe eee 8-eeeeeeeeeeeee. M eeee ee eee eeeee (8.88e, 8.88eeee) ee MMM (88eM) eee eeeeee ee 88°M eee e 8.8M eeee ee MMM ee MMM (88eM, 88.8eeee) eeeeeee eeee eeeeeeeeeee eee eeeee eeee e eeeeeee. Mee eeeeeee eee eeeeeee eee 88eee ee 88°M, eeeeee ee ee, eee eeeeeeee eeeee M8 eee 8e. Me eee eeee eeeeee ee ee eee eee eeeeeeee eee eeeeeeee eeee M8M (8eM). Mee eeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeeeee eeeeeee M8M (88eM) eee MM8Me8 (888eM). Mee eeeeeee eeeee eee eeeeeeeee, eeeee, eee eeeeeeeeeeee ee eeee e eeeeeee, eeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeee 8:88) ee eeee e eee eeeee; eeeee: 8.88e (88%); ee 888°M (MeMMe/eeeeee).

References