Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login to access the full content or check if you have access via
1.1.1.1.1.1.2.4 Arenesulfonate Electrophiles

DOI: 10.1055/sos-SD-207-00004

Guram, A. S.; Milne, J. E.; Tedrow, J. S.; Walker, S. D.Science of Synthesis: Cross Coupling and Heck-Type Reactions, (2013168.

The trifluoromethanesulfonate activating group remains the workhorse for C—O activation in aryl and vinyl electrophiles, but the expense of the common reagents used to install the trifluoromethanesulfonate group (Tf2O, PhNTf2, etc.) and the limited stability of the trifluoromethanesulfonate group toward hydrolysis have spurred significant effort in alternative activation modes. As reactivity toward oxidative insertion with a transition metal parallels the pKa of the corresponding leaving group acid, arenesulfonate groups[‌108‌] (specifically 4-toluenesulfonate) have received significant attention as a trifluoromethanesulfonate replacements (PhSO3H pKa = −2.8; TfOH pKa = −5.9; MsOH pKa = −1.9).[‌109‌]

Meee 8-eeeeeeeeeeeeeeeee eee eeeeee eeeeeeee eeee eee eeeeeeeeeeeee eeeeee eeeeeeeee ee eeeeeeeee eeee eeeeeeeeeee eee eeeeeeeeeee eeeee eeeeeeee. Meee 8-eeeeeeeeeeeeeeeee eee eeeeeeeeeeeee eeee eeeeee eeeeee eeeeeeeeee eeee eeeee eeeeeeeeeeeeeeeeeeeeeeeee eeeeeeeeeeee. Me eeeeeeee, eeee 8-eeeeeeeeeeeeeeeee eee eeeeeeeeeeeee eeee eeeeeeee ee eeeeeeeee-eeeeeeeee eeeee-eeeeeeee eeeeeeeee eee eeee ee eeeeeee eeee eeeeeeeeeee eee eeeeeeee-eeee eeeeeee ee eeeeeee eeeee eeeeeeee eeee eeeeeeeeeee eeeee. Meeeeee eeeeeee eeee eee eeeeeeeee-eeeeeeeee Meeeee–Meeeeee eeeee eeeeeeeee eeee eeee 8-eeeeeeeeeeeeeeeee eeeeeee eee eeeeeee(eeeeee)eeeeeeeee eeeeee eeeeeeeeeeee (Meeeee 88).[‌888‌,‌888‌]

Meeeee 88 Meeeeee Meeeeee Meee ee Meeeeeeee-Meeeeeeee Meeee Meeeeeeee eeee Meee Meeeeeeeee eee Meeeeeeeeee Meeee[‌888‌,‌888‌]

8-(Meeeeeeeeeeeeeeeeeeee)-8′,8′,8′-eeeeeeeeeeeeeeeeeeee (MMeee) ee e eeeeeee-eeeeeee eeeeee eee eee Meeeee–Meeeeee eeeeeeee ee eeee 8-eeeeeeeeeeeeeeeee eeee e eeeeeee ee eeeeeeeeeeeeee eeeeeeeeeee eeeee ee eeee eeeeeee 88.[‌888‌] Mee eeeeeeee eeeeee ee eeeeeeee ee eeeeeeee-eeeeeeeeeee eee eeeeeeee-eeeeeeee eeeeee, ee eeee ee eeeeee eeeeeeeee, ee eee eeeeeee eeee. Meeeeeee eeeee eee eeeeeeeeeeeee eeeeeeee ee eeeee eeeeeeeeeeee ee eee eeee 8-eeeeeeeeeeeeeeee. Meeeeee 8-eeeeeeeeeeeeeeeee eeee ee 8-eeeeeee, 8-eeeeeeee, eee eeeeeeeeeeee-8-ee 8-eeeeeeeeeeeeeeeee eeeeeee eeee eeee e eeeeeee ee eeeeeeeee eeeeeee eeeee. M eeeee ee eeeeeeeeee eeeeee eee eeeeeeeee ee eeee eeeeeeee eeeeeee eeeeeeeee eeeeeeee, eeeee, eeeee, eee eeeeee (Meeee 88, eeeeeee 8–8). Meeeeeeee eeeeeeee eeeeeeeee eeee eeee 8 ee 8 eee% eeee e eeeee/eeeeee eeeee ee 8:8.8. Meeeeeeee eee eeeeeeeee eeeee eeeee, eeeeeeee eeeeeeeeee ee eeee eeee 8 eeeee ee 88 °M ee eeeeeeeeeeeeeee. Meee eeee eeeeeeee eeeeee, eeeeeeeee eee eeeeeeeeeee eeeee eeeeeee eeee eee 8-eeeeeeeeeeeeeeee.

Meeeeee ee eeeee ee eee 8-(eeeeeeeeeeeeeeeeeeeee)-8′,8′,8′-eeeeeeeeeeeeeeeeeeee (MMeee) eeeeeeee eeeeee, 8-[8-(eeeeeeeeeeeeeeeeeeeee)eeeeee]-8-eeeeee-8M-eeeeee (MM-Meee), eeeee eee eeee eeeeeeee eeee eeee eeeeeeeeeeee eeeeeeeee ee Meeee Meeeeeeee, ee e eeeeeee eeeeee ee eeeeeeeee-eeeeeeeee eeeee eeeeeeee ee eeee eee eeeeeee 8-eeeeeeeeeeeeeeeee eeee eeeeeeeeeee eeeee.[‌888‌] Me eeee eee MMeee eeeeee, eeee eeeeee eee eeeeeeee eee eeeeeeee-eeeeeeeeeee eeeeee ee eee eeee 8-eeeeeeeeeeeeeeeee, eee eeeeeeee-eeeeeeee eee eeeeeeeeee eeeeeeee eeeeeee eeeee eee eeee eeeeeeeee (Meeee 88, eeeeeee 8–88). Meeeeee eeeee eeee eeeeeeee-eeeeeeeeeee eeeeee eee eeeeee ee eeee eeeeeeeeee. Meeeeeeee eeeeeeee eee eeeeeeeee eeee eeee 8 eee% eeee e eeeeeeeeee eeee eeeee/eeeeee eeeee ee 8:8. Meeeeeeee eee eeeeeeeee ee eeeeeeeee eeee-eeeee eeeeeee eeee eeeeeeeee eeeeeeeee ee eeee eee eee eeeeeeeee eeeeeeee ee <8 eeeee ee eeeeee eeee eeeeee ee eee eeeeeee eeeeeee 88 (88–88% eeeeeeee). Mee eeeeeeee eeeeee ee eeeeee eeeeee eee eee eeeee eeeeeeee ee 8-eeeeeeee 8-eeeeeeeeeeeeeeee eeee eeeeeeeeeeeee eeee ee eeeeeee eeeeeeeeeee; eeeeeee, eee eeeeeeee eeee ee 88 eeeee ee eeeeeeeeeeeeeee eeee ee eeeee eeee eeeeeeeeee (Meeee 88, eeeee 88).

M eee eeeeeeeeee ee eeeeeeeeeeeeeee, 8-(eeeeeeeeeeeeeeeeeeeee)-8′,8′,8′-eeeeeeeeeeee-8,8-eeeeeeeeeeeeeeeee (MeeeeMeee), ee eeeeeee ee eeeeeeee eeee 8-eeeeeeeeeeeeeeeee eee eeee eeeeeeeeeeeeeeeee (eeee eeeee) eeee eeeeeeeeeee eeeee (Meeee 88, eeeeeee 88–88).[‌888‌] Meeeeeee-eeeeeeeee eee eeeeeeeeee eeeeeeee eeeeeee eeeee eeeeee eeee ee eeeeeeeee eeeeee ee eee eeeeeeee eeeeeeee (eeee ee 8.8 eee% Me). Mee eeeee ee eee eeeeee eeeeeeee e eeeee eeee ee eeeeeee eeeee eee eeeeee eeeeeeeee eeeeeee eeeeeeeee eee eeeeeeeeeeee eeeee, eeeee eee eeeeee eee eeeee ee eeee eeeeee.

Meeee 88 Meeeeeeee-Meeeeeeee Meeee-Meeeeeee Meeeeeeee ee Meee 8-Meeeeeeeeeeeeeeee eeee Meeeeeeeeee Meeee[‌888‌‌888‌]

Meeee Me8 Me8 Meeeeeeeee Meeee (%) Mee
8 Me Me(MMe)8 (8 eee%), MMeee (8 eee%), M8MM8M8M (8 eeeee), MMM, 88 °M, 8 e 88 [‌888‌]
8 8-M8MM8M8 Me(MMe)8 (8 eee%), MMeee (8 eee%), M8MM8M8M (8 eeeee), MMM, 88 °M, 8 e 88 [‌888‌]
8 8-eeeeeee 8-M8MM8M8 Me(MMe)8 (8 eee%), MMeee (8 eee%), M8MM8M8M (8 eeeee), MMM, 88 °M, 8 e 88 [‌888‌]
8 8,8-(MeM)8M8M8 Me(MMe)8 (8 eee%), MMeee (8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 88 °M, 8 e 88 [‌888‌]
8 8,8,8-eMe8M8M8 Me(MMe)8 (8 eee%), MMeee (8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 88 °M, 8 e 88 [‌888‌]
8 Me(MMe)8 (8 eee%), MMeee (8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 88 °M, 8 e 88e [‌888‌]
8 Me Me(MMe)8 (8.8–8 eee%), MM-Meee (8–8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 888 °M 88 [‌888‌]
8 8-MeM8M8 8-Mee Me(MMe)8 (8.8–8 eee%), MM-Meee (8–8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 888 °M 88 [‌888‌]
8 8-eeeeeeee 8-Mee Me(MMe)8 (8.8–8 eee%), MM-Meee (8–8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 888 °M 88 [‌888‌]
88 8-eeeeeeee Me(MMe)8 (8.8–8 eee%), MM-Meee (8–8 eee%), M8MM8M8M (8 eeeee), e-MeMM, 888 °M 88 [‌888‌]
88 8-eeeeeeee Me Me(MMe)8 (8.8–8 eee%), MM-Meee (8–8 eee%), M8MM8M8M (8 eeeee), MMM, ee, 88 e 88 [‌888‌]
88 8,8,8-Me8M8M8 8,8-(MeM)8M8M8 Me(MMe)8 (8 eee%), MeeeeMeee (8 eee%), M8MM8M8M (8 eeeee), MeMMe8MM, 888 °M 88 [‌888‌]
88 8-e-MeM8M8 8,8-Me8M8M8 Me(MMe)8 (8.8 eee%), MeeeeMeee (8.8 eee%), M8MM8M8M (8 eeeee), MeMMe8MM, 888 °M 88 [‌888‌]
88 8M-eeeee-8-ee Me(MMe)8 (8 eee%), MeeeeMeee (8 eee%), M8MM8M8M (8 eeeee), MeMMe8MM, 888 °M 88 [‌888‌]

e 88–88% eeeeeeeeee ee Me8MMe.

Me eeeeeeee ee eeeeeeeee, eeeee eeee eeeeeeeeee eeeeee eeee eeee eeeeeeeeeeee ee eee eeeeeeee ee eeee 8-eeeeeeeeeeeeeeeee. Mee ee eee eeee eeeeeeeeee eeeeeeeeee eeeeee eeeee eeeeeeeeeee eeeeeeeee eee eeee ee eeeeeee eeeeee-eeeee eeeeeeeee (eeeeeee–M-eeeeeeeeeeee eeeeeee eeeeeeeee eee eeee eeeeeeeeeeeeee eeeeeeeee eeee eeeeeeeeeee eeeee eeee eeee eeee eeeeeeee[‌888‌]). Meeeee eee ee eeeeeeeee eeee eeeee eeeeeeeeee eeeeee ee eee eeeee eeee[‌888‌] eeeeee eeeeeeeee ee eeeeeee eee eeeeeeeee eeeeeeeeee eeeeee eeeeeeeeeeeee eeee eeeeeeeee eeeeeeeeeeeee ee eeeeeeeee-eeeeeeeee eeeeeeeee. Meeeee eeeeeeeeeeee, eeeeeee, eeee ee ee eeee ee eeeeeeee eeeeeee eeeeeeeee eeeeeeee eeeeee [e.e., MeMe ee Me(8)] ee eeee eeeeeee eeeee ee eeee eeeeeeeeeeee (>888 °M). Meeeeeeeee eeeeeeee ee 8888, [8,8′-eee(eeeeeeeeeeeeeeeee)eeeeeeeee]eeeeeeeeeeeeee(MM) [MeMe8(eeee)] ee eeeeee eeeeee eee eeeee eeeeeeee ee eeee eeeeeeeeee eeee eeeeeeeeeeeee eeee ee eee eeeeeeee ee eeee eeeee ee eeeeee eee eeeeeeee eeee eee eeeeee eeeee.[‌888‌]

Mee eeeeee eeeeeeee eeeeeeeeeee(eeeeeeeeeeeeeeeeeeeeee)eeeeee(MM) [MeMe8(MMe8)8] ee eeee ee eeeeee eeeee-eeeeeeee eeeeeeeee eeee eeee 8-eeeeeeeeeeeeeeeee eee eeeeeeeeeee eeeee ee eeeeeeeeee eee eeeeeeee eeeeeeee (8.8–8.8 eee% Me).[‌888‌] Meee eeeeeeeeeee, eee eeeeeeee eeee eee eeee ee eeeeeeee eeeeeeee eeeee ee ee eeeeeeeee. Mee eeeeeeeee eee eeeeeeeee ee eeeeeee ee eeee eeeeeeeeeeee (888 °M) eee eeeeeeee eeeeeee ee eeee (88–88 eeeee) eee eee eeeeeeee ee eeeeeeee-eeeeeeee eee eeeeeeee-eeeeeeeeeee eeeeeeeeee eeeeee ee eee eeee 8-eeeeeeeeeeeeeeee. eeeee-Meeeeeeeeee eeee 8-eeeeeeeeeeeeeeeee eeee eeeee eeeeee, eee eee eeeee ee eee eeeeeee eeee eeeeeeee eee eeee eeeeeee ee eeeeeeee-eeeeeee ee eeeeeeee-eeee eeeeeeeeeeee. Mee eeeeeee eeeeeeee eeeeee [8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee]eeeeeeeeeeeeee(MM) [MeMe8(eeee)] ee eeeeeeeee ee eeeee eeeeeeee ee eeee 8-eeeeeeeeeeeeeeeee ee eeeeeee eeeee eee eee eeeeeeee eeeeeee (8 eee%).[‌888‌]

Me eeeeeeee eee eeeeeee eee eeeee ee eee eeeeee eeeeeeeee Meeeee–Meeeeee eeeeeeee ee eeee 8-eeeeeeeeeeeeeeeee, eeeeeeee eeeeee eeee eeeeee eeeeeeeeee ee eeeeee eee eeeeee eeeeee(8) eeeeeeee eeee eeeeeee. Meeeeeee eeee eeeeee(8) eeeeeeee [ee Me(eee)8] ee eee eeeeeeee ee eeeeee eeeeeeeeeeeeeeeeeeeeee eeeeee eeeeeeee ee eeee 8-eeeeeeeeeeeeeeee eeeeeeeeeeeee eeee eeeeeee eeeee ee eeeeeee eeeeeeeeeee.[‌888‌] Meee 8% eeeeeeee eeeeeee, e eeeee ee eeeeeeee-eeee eee eeeeeeee-eeee 8-eeeeeeeeeeeeeeeee eee ee eeeeeee ee eeeeeeeee eeeeee (88–88%).

Mee ee eeeeee(8) eeeeeeeee ee eeeeeeeeeeee ee e eeeeeeeee eeeee ee eeeee eeeeeee eee eeeeeeeeeee, ee eeee ee eeee eee eeeeeeeee eeeeee. σ-Meeeeeeeee(MM) eeeeeeeee eee eeeee eeeeeeeeeee ee eeeeeeeeeeee.[‌888‌] Meeeeeee ee eee eeeeeeeeee eeeeeeeee eeee eeeeeee eeeee eeeeeeee eeeeeee eee eeeeeeeeeeeee eeeeee eeeeeeee ee eeeeeeee ee eee eeeeeee eeeeee(8) eeeeeeee. Meeee eee eeeeee eeeeeeee eee eee- eee eeeeeeee-eeeeee eeeee-eeeeee(8-eeeeeeee)eee(eeeeeeeeeeeeeeeeee)eeeeee(MM) (88), eeee eee eeeeeeee ee eeeeeeeeeeeeeeeeeeeeee (ee eee eeeeeeeeeeeeeeeee eeee), eeeee eeeeeeee ee eeee 8-eeeeeeeeeeeeeeeee 88 eeee eeeeeee eeeee 88 ee eeee eeeeeee 88 eeeeee eeeeeeee ee eeee eeeeeeeeeee ee 88 eeeee. Mee eeeeeeee eeeeeeeeee eee eeee (eeeeeee/eeeee eeee eeeeeeeee eeeeeeeee eeee) eee eeeeeeee eeee eeeeeeee-eeeeeeeeeee eee eeeeeeee-eeeeeeee eeeeee ee eee eeee 8-eeeeeeeeeeeeeeee (Meeee 88). eeeee-Meeeeeeeeee eeee 8-eeeeeeeeeeeeeeeee eeeeee eeeee eeeeee, eee eee eeeeeeee eeeee eeeeeee ee ee eeeeeee ee eeee eeeee eeee eeeeeee ee eee eeeeeeeeeee eeee.

Meeee 88 Meeeee-Meeeeeeee Meeee-Meeeeeee Meeeeeeee ee Meee 8-Meeeeeeeeeeeeeeee eeee Meeeeeeeeee Meeee ee Meee Meeeeeeeeee[‌888‌]

Meeee Me8 Me8 Meeee (%) Mee
8 8-MeMM8M8 Me 88 [‌888‌]
8 8-MeMM8M8 Me 88 [‌888‌]
8 8-MMM8M8 Me 88 [‌888‌]
8 Me 88e [‌888‌]
8 Me 88e [‌888‌]
8 8-Mee 8-Mee 88 [‌888‌]
8 8-MeMM8M8 8-Mee 88 [‌888‌]

e Meeeeeee eee ee 88 °M eee 88 e.

e Mee eeeeeeeee eee 8,8-eeeeeeeee eee(8-eeeeeeeeeeeeeeee), 8 eeeee ee eeeeeee eeee eee eeee, eee eee eeeeeee eee 8,8′:8′,8′′-eeeeeeeee.

M eeeeeee eeeeeeeeeee, (8-eeeeeeeeeeeee)(eeeeeeee)eee(eeeeeeeeeeeeeeeeeeeeee)eeeeee(MM) [(8-MeMM8M8)Me(MMe8)8MMe], eeee eeeeeee eeeeeeeee eeeee eee eeee eeeeeeeeeee Meeeee–Meeeeee eeeeeeeee eee eeee eeeeeeee.[‌888‌]

Meeeeeeeeeee Meeeeeeee

Meeeeee (Meeee 88, Meeeeee 88–88); Meeeeee Meeeeeeee:[‌888‌]

Me eeee-eeeee eeeee-eee eeeee eeee eeee (88 eM) eeeeeeee eeee e eeeeeeee eeeeeee eee eee eeeeeee eeee Me(MMe)8 (8.8 ee, 8.88 eeee), MeeeeMeee (88.8 ee, 8.88 eeee), eee 8-eeeeeeeeeeeeeeee (8.8 eeee), eee eeeeeee eeee (8.8 eeee), eee M8MM8•M8M (8.8 eeee). Mee eeee eeee eee eeee eeeeeee eeeeee eeee e Meeeee-eee eeeeeee eeeee eee eee eeeeeeeee eee eeeeeeeeee eeee eeeee (8 ×). 8-Meeeeeeeeee-8-ee (8 eM) eee eeee eeeee ee e eeeeeee eeeee e eeeeeeee eeee ee eeeee. Mee eeeeeee eee eeee eeeeeee ee ee eee e eee eeeeeee ee eeeeee e eeeeeeeeeee eeeeee, eee eeee eeeeeeeeeee ee e eeeeeeeee eee eeee eee eeeeeee eeeee MM eeeeeeee eeeeee eeeeeeee eeeeeeeeeee ee eee eeeeeeee 8-eeeeeeeeeeeeeeee. Meee eee eeeeeeee eee eeeeeeee (eeee eeeeeeeee eeee eeeeeeee ee eeee eeee 8 e), eee eeeeeee eee eeeeeee eeee M8M (8–8 eM) eee MeMMe (~8 eM). Mee eeeeeee eeeee eee eeeee (MeMM8) eee eeeeeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (Meeeeee eeeeee eee MMMM eeeeee 88 e).

Meeeeee 88; Meeeeee Meeeeeeee:[‌888‌]

Me eeee-eeeee 88-eM eeeee-eeeeee eeeee eee eeeeeee eeee M8MM8 (8 eeee), eeeee-eeeeee(8-eeeeeeee)eee(eeeeeeeeeeeeeeeeee)eeeeee(MM) (88; 8.88 eeee), eee Me8M•MMM8 (8.888 eeee). Meee, eee eeee eeeeeeeee 88 (ee eeeee; 8 eeee) eee eeeeeeeeeee eeee 88 (8.8 eeee) eeee eeeee. Mee eeeee eee eeeeeeeee eee eeeeeeeeee eeee M8 (8 ×). Mee eeee eeeeeeeee (ee eeeeee; 8 eeee), eeeee eeeeeee (8 eM), eee eeeeeeee M8M (8.88 eM) eeee eeeee eeeeeee e eeeeeee ee eeee eeee. Mee eeeeeee eee eeeeeee ee ee eee 88 e eee eeeeeeee eeeeeee e eee ee eeeeee eee, eeeee eee eeeeee eeee MeMMe. Mee eeeeeee eee eeeeeee eeee eee eeeeeeee eeeeeee eeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).

References


Cookie-Einstellungen