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6.1.7.6 Methods 6: Additional Methods

DOI: 10.1055/sos-SD-006-00221

Miyaura, N.Science of Synthesis, (20056281.

Many boronic acids are stable toward air and water, and the BC bond is inert to many electrophiles under neutral or acidic conditions that allow the functionalization of the parent arylboronic acids. The radical bromination at the benzylic hydrogen of 4-tolylboronic acid with bromine or N-bromosuccinimide gives [4-(bromomethyl)phenyl]boronic acid (71) without affecting the boryl group (Scheme 21).[‌124‌] The nitration of 4-tolylboronic acid with fuming nitric acid is used for the synthesis of (4-methyl-3-nitrophenyl)boronic acid (72) which can be converted into its amino derivatives by catalyzed hydrogenation in the presence of platinum(IV) oxide.[‌125‌,‌126‌] The weakly electron-withdrawing property of the boronic acid group (σp=0.12) directs the electrophilic substitution at the meta position. The carboxylic acid derivative 73 is synthesized by potassium permanganate oxidation.[‌127‌] Again, the BC bond remains intact during the oxidation of the methyl group.

Meeeee 88 Meeeeeeeeeeeeeeee ee Meeeeeeeeee Meeee[‌888‌‌888‌]

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

Meeeee 88 Meeeeeeeeeee ee Meeeeeeeeeeee eee Meeee-Meeeeeee Meeeeeeee[‌888‌,‌888‌]

Meeeee eeeeeeeeeeee eeeee eee eeeeeeeee ee eeee-eeeeeee eeeeeeeeee eeeeeeeee ee eeeeeeeeeeee eeeee eee -eeeeeeeee. M eeeeeeeeee eeeeeeeee eeeeeee 88 eeeeeeeee eee eeeeeeeeeee ee eeeeeeeeeeee eeee 88 ee eeee eeeeeeeeeee eeee eeeeeeeee ee 8 eeeeeeeeee ee eeeeee ee eee eeeeeeeee ee eeeeee eeeeeeeeeeee eeee 88 ee 88% eeeee (Meeeee 88).[‌888‌] Meeeeeee eee eeeeeee eeee eeeeeeee eeeeeeeee eeeeee ee eeeeeeee eeeeee, eeeeeee eeee-, eee-, eee eeeee-eeeeeeee eeeeeeeeeee ee eeeeeeeeeeee eeeeeeeee, eeee ee eeeeeeeeeeeee 88, eee eeeeeeeeeee ee eeee eeeeee eeee eee eeeeeeeeeeeee eeeeeee eeeeee. Meeeeeeeeeeee, eee [8+8] eeeeeeeeeeeee ee eeee-8,8-eeeeeeeeeeeee eeee eeeeeee, ee eeee ee eeeeeeeeeeeeee eeee 8,8-eeeeee, ee ee eeeeeeeee eeeeee eee eee eeeeeeeee ee eeeeee eeeee- ee eeeeeeeeeeee.[‌88‌,‌888‌‌888‌] Mee eeeeeee, eeeeeeee(eeeee)eeeeeee eee eeeeee eeeeeeeeeee eeeeee eeeeeeeeeeeeeee, eeeeeeee, eee 8,8-eeeeeeeeeeee-8,8-eeeee, eeeeeeee eeee eee eeeeeee eeeeeeeeeeeeee eee eeeeeeeeeeeeeeeeee eee eeeeeeeeeeeeeee eeeeeeeeeee 8,8-eeeeee. Meeeee 88 eeeee eee eeeeeeeee ee eeeeeeee-8-ee-8-eeeeeeeee eeee 88 eeeee eeee eeeeeeeeeee.[‌888‌]

Meeeee 88 Mee Meeeeeeee ee Meeeee Meeeeeeeeeeeee Meeee[‌888‌,‌888‌]

Mee eeeeeeeee ee e eeeeeeeee eeeeeeeee ee (8-eeeeeeeee)eeeeeeeee ee eeee eeeeeeeeeeee eee eeeeeeeeeeeeee eeeeee eee eeeeeeee eee eeee eeeeeeeee eeeee eeeeeeeee eee eeeeee eeeeeeeeeeee eeeee.[‌8‌,‌8‌] Mee eeeeeee, (8M,8M)-8,8-eeeeeeeeeeee-8-eeeeee-8,8,8-eeeeeeeeeeeee (88) eee ee eeeeeee eeee (eeeeeeeeeeeeee)eeeeeee ee eee eeeeeeee ee eeee(MM) eeeeeeee eeeeeeee ee eeeeeee eeeeeeeeeeeeeeeee ee eeeee M-eeeeeeeeeeeee 88 (Meeeee 88).[‌88‌] Meeeeeeeeeee ee eeeeeeeeeeee ee eeeeeeee eeee 8-{[eeee(eeeeeeeeeeeee)eeeeee]eeeee}eeeeeeeeeeeeeee eeee (MMMM) ee eeeeeee 8M eeeeee eeeeeeeee ee eeee eeeeeeeeeee, eeeeee eeeeeeeeeeee eeee 88 eeeeeeeeeeeeee. Meeeeeeeeeeee, eeeeeeeee ee 8,8,8-eeeeeeeeeeeee 88 ee eeeeeee (8-eeeeeeeee)eeeeeeeee eeee eeeeeeeeeeeee eeeeeeeee eeeeeeee eeeee- ee (8-eeeeeeeeee)eeeeeeeee eeee eeee eeeeeeeeeeeeeeeeee. Meee eee ee eeee ee eeeeeeeeee [(8M)-8-eeeee-8-eeeeeeeeeee]eeeeeee eeee, eeeee eee ee eeeeeeeee eeee eee eeeee-eeeeeeeeee eeeeeee 88, eee eeee eeeeee eeeeeeeee ee eeeeee eeeeeeeee.[‌888‌]

Meeeee 88 Meeeee Meeeeeeeeeee Meeee eee Meeeeeeeeeee ee (8-Meeeeeeee)eeeeeeeee[‌88‌,‌888‌]

Meeeeeeeeeee Meee

[8-(Meeeeeeeeee)eeeeee]eeeeeee Meee (88):[‌888‌]

MMMMMMM: Meeeeee ee e eeeeee eeeeeeee ee eee eeee, eeeeee eeeeeeeee, eeeee, eee eeee. Meeeee eeeeeee eeeeee eeeeee eee eeeeeee eeeee ee eeeeeee eeee eeee eee eeee.

Mee-eeeee 8-eeeeeeeeeeee eeee (8e, 88.8eeee) eee MMe8 (888eM) (MMMMMMM: eeeee) eeee eeeeeee ee ee eeee-eeeee eeeee, eee e eeee ee Me8 (8e, 88.8eeee) ee MMe8 (88eM) eee eeeeeee ee e eeeeeeee eeeeee. Mee Me8 eeee (ee. 8eM) eee eeeee eee e 888-M eeeeeeee eeee eee eeee eeeeee eeee eee eeeee. Meeee ee eeeeeeeee eeeeee eeeeeee eeee 8 ee 88eee, eee eeeee ee eee eeeee Me8 eeeee. Mee eeeeeeeee ee eee Me8 eeee eee eee ee eeeeeeee (8eM) eeee e eeeeee ee eeeee 88eee. Me eee eee ee eee eeeeeeee, eeee ee eee eeeeeee eee eeeeeee eee eee eeeeeee eee eeeeeeeee eee eeeeeeeeeeeeee (MMMe8); eeeee: 8.8e (88%).

(8-Meeeee-8-eeeeeeeeeee)eeeeeee Meee (88):[‌888‌]

Me eeeeee MMM8 (e=8.88, 88eM) eee eeeee e eeeeee eeee eee eee eeeeeee eee eeeeee ee 88°M. Mee-eeeee 8-eeeeeeeeeeee eeee (88e, 88.8eeee) eee eeeee eeeeee eee eeeeee ee 88e eeee eeee eeeeeeeeee eeeeeeee, eeeeeee eee eeeeeeeeeee eeeeeee 88 ee 88°M. Meeee eeeee eeeeeee eee 8888eee, eee eeeeeee eee eeeeeeeee eeeeee eeee eee (888888e). Mee eeeeeeeeeee eee eeeeeeeee ee eeeeeeeeee, eeeeee eeee eeeee eeeeeeee ee eee eeeee, eee eeeeeeeeeeeeee (eeeee eeeeee ee M8M) ee eeee eeeeee eeeeeee; eeeee: 88e (88%).

8-(Meeeeeeeeeeeee)-M-eeeeeeeeeeeee (88):[‌888‌]

Me e eeeee eeeeeee eeee Me/Me (888ee) eee eeeee e eeee ee eeeeee M-(eeee-eeeeeeeeeeeeee)-8-eeeeeeeeeeeee (888ee, 8.88eeee) ee eee eeeeeee (8.8eM) (MMMMMMM: eeeeeeeeee), eeeeeeee ee MMM (8.8eM). Mee eeeeeee eee eeeeeeeee eeeee eee eeeeeeeeeeeee eee eeee eeeeeeee, ee eeeeeeeeee ee MMM eeeeeeeeeeee. M eeee ee eeeeeeeeeeee 88 (888ee, 8.88eeee) ee eee eeeeeee (8.8eM), (8-Mee)8M (88ee, 8.88eeee), eee Me(MMe)8 (88ee, 8.88eeee) eeee eeee eeeee, eee eeeeeee ee 88°M eee 8e. Mee eeeeeeee eee eeeeeee eeee MeMMe (8eM) eee eee eeeee eee eeeeeee ee eeeeeeeeee. Mee eeeeeeee eee eeeeee eeee 8M ee MMe (88eM), eeeee, eee eee eeeeeeeee eeee eeeeeee eeeee eeeeee eeeeeee eeeeeee. Meeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8) eeee eeeeeeeeeeee 88 ee e eeeee eeeee (888ee, 88%). M eeee ee eeeeeeeeeeee 88 (88ee, 8.888eeee) ee MeMM/MeMM (8:88, 8.8eM) eee eeeeeeeeeeee eeee 88% Me/M (88ee) eee 88e. Mee eeeeeeee eee eeeeeee ee eeeeeeeeee eeeeeee Meeeee eee eee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeee eeeee eeee eeeeeeee eee eeeeeeeee ee MM8Me8 (8eM) eee MMM (8.8eM, 8.88eeee) eee eeee eeeee. Mee eeeeeee, eeeeeeeee eeee eeeee ee Me eeee, eee eeeeeee eee 8e. Mee eeeeeeeee eeee eeeeeee ee eeeeeeeeeee, eeeeeeee ee eeeeeeeeeeeee eeee eeeeeee ee eeeeee eeeeee ee MMM. Mee eeeeeee eee eeeeeeeee ee M8M eee eee eM eee eeeeeeee ee 8.8 eeee 8.88M ee MeMMM8. Mee eeeeeee eee eeee ee 8°M ee eeeee eeeeeeee.

Meeeeeee-8-ee-8-eeeeeeeee Meee (88); Meeeeee Meeeeeeee:[‌888‌]

Me e eeee ee eeeeeeeeeeee eeee 88 (88ee, 88μeee) ee eeeeeee (88.8eM) (MMMMMMM: eeeeeeeeee) eee eeeee eeeeeeeeee eeeeeeeee eeeeeee 88 (8ee, 8.8μeee) ee eeeeeee (8eM). Mee eeeeeeeee eeeeeee eee eeeeeee ee ee eee 8e, eeeeeee ee eee eee 88eee, eee eee eeeeeee eee eeeeeee ee eeeee. Mee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeeeeeeee eeeeee eee eeeee, MeMMe/eeeeee 8:8) ee eeee e eeeee eeeee; eeeee: 8.8ee (88%).

(8-Meeee-8,8-eeeeeeeeeeeeeeee-8-ee-8-ee)eeeeeee Meee (88):[‌888‌]

(Meeeeeee[(8M)-eee-8-ee-8ee]eeeeee eee eeeee ee 8,8-eeeeeeeeeeee-8,8-eeeee (8.88.8 eeeee) ee eeeeeee ee ee eeeee eeeee. Mee eeeeeee eee eeeeee ee 888°M eee 8e ee e eeeeee eeee. Meeeeee MeMM eee eeeee ee ee, eee eee eeeeeee eeee eeee eeeeeeee eee eeeeeeeee eeee eee eeeeeeeeeeeee eeeeeee eeeee ee eeeeeeeee eeee eeeeeee.

[(8M)-8-(Meeeeeeee)eeeee]eeeeeee Meee (88):[‌88‌]

Me e eeee ee MM8Me8 (88eM, 8.888eee) ee MMM (888eM) eee eeeee 8.88M MeMe (888eM, 8.888eee) ee 888°M. Meeee 8eee, e eeee ee 8,8,8-eeeeeeeeeeeee 88 (88.8e, 8.888eee) eee eeeee eee eeeeeee. Meeee 88eee, eeeeeeee MeMe8 (88e, 8.888eee) eee eeee eeeee. Mee eeeeeee eee eeeeeee ee eeee ee ee eee eeee eee 88e. Mee eeeeeeeee eeee eee eeeeeeeeeee ee e eeee ee MeMMe, eeeee eee eeeeeeee ee eeeeee 8.88M MeMe (888eM, 8.888eee), eeeeeeee ee MMMM (88eM), ee e eeee ee MeMM (88eM, 8.888eee) ee MMM (888eM) ee 88°M. Mee eeee eee eeeeee ee ee, eeeeeee eee 88e, eee eee eeeeeee eee eeeeeee ee eeeeeeeeeeee. Meeeee (888eM) eee ee MM8Me (888eM) eeee eeeee ee eee eeeeeee. Mee eeeeeee eeeee eee eeeeeeeee, eeeeee eeee eeeee, eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeee eeeee eeeeeeeeeeeee 88. M eeee ee eeeeeeeeeeeee 88 (88e, 8.888eee) ee Me8M (888eM) eee eeeeeee eeee MMMM (88e, 888eeee) ee 8M ee MeMM (888eM) ee ee eee 88e. Mee eeeeeee MeMM eeeeeeeeee eee eeeeeee eeee eee eeeeeeeee ee eM<8 ee eeeeeeee ee 88M MMe. Mee eeeeeee eee eeeeeeeee eeee MeMMe (888eM), eeeee (MeMM8), eee eeeeeeeeeeee ee eeeee; eeeee: 88.8e (88%).

References


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