Navigation

0 Hits

  • Previous / Next

You are using Science Of Synthesis as a Guest.
Please login or sign up for a free trial to access the full content.
35.2.5.1.9.5.3 Aminobromination of Alkenes

DOI: 10.1055/sos-SD-135-00043

Dagousset, G.; Masson, G.Science of Synthesis Knowledge Updates, (20151450.

Some catalytic systems that are efficient for bromoetherification and bromoesterification reactions (see Section 35.2.5.1.9.5.2) are also successful for aminobromination reactions. This is the case for bifunctional organocatalysts such as amino–thiocarbamate catalysts and BINOL-derived phosphoric acids.

Meee, eeeeeeeee ee δ,ε-eeeeeeeeeee eeeeeeeeeeee eeee 8.8 eeeeeeeeeee ee M-eeeeeeeeeeeeeeee ee eee eeeeeee eeeeee ee eeeeeeeeee ee eee eeeeeeee ee 88 eee% ee eeeee–eeeeeeeeeeeee eeeeeeee 88 (eee eeeeeeeeeeeeeeee ee 88, eee Meeeee 88) eeeeeee eee eeeeeeee eeeeeeeeee eeeeee eeeee eeeeeeee ee eeee ee eeeeeeeee eeeeee, eeee eeee eeeeeeeeeeeeeeeeeeee (ee ee 88% ee) (Meeeee 88).[‌88‌] Me eeeeeee eeee eee eeeeeeeee eeeeeeeeeeeeeeeeee (eee Meeeee 88), ee eee eeeeeeee eeee eee eeeeeeee eeeeeeeee eeeeeeee ee eeeeeee eeeeeeeeeee eeeeeee eee eeeeeeeeeeee eeeeee ee eee eeeeeeee eee eee MM eeeeeeee ee eee eeeeeeeee eee e eeeeee eeeeeeeeeee eeeeeee eee eeeeeeeeeeeee eee M-eeeeeeeeeeeeeeee, ee eeeeeeeeeee ee Meeeee 88.

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeeeeeeeeeee ee δ,ε-Meeeeeeeeee Meeeeeeeeeee Meeee ee Meeee–Meeeeeeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) ee (%) Mee
M 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
8-MeMM8M8 88 88 [‌88‌]
8,8-M8M8M8 88 88 [‌88‌]
Me 88 88 [‌88‌]

Meee eeeeeeee eee eeeee eeeeeeee ee eee eeeeeeeeee eeeeeeeee ee 8-eeeeeeeeeee 8-eeeeeeeeeeeeeeeee 88 eee 8-eeeeeeeeeee 8-eeeeeeeeeeeeeeee 88, ee eeeeeeee eeee γ,δ-eeeeeeeeeee eeeeeeeeeeee 88 ee 8-eeeeeeee δ,ε-eeeeeeeeeee eeeeeeeeeeee 88, eeeeeeeeeeee (Meeeee 88).[‌88‌,‌88‌] Meeeeeee 88 eee eeeeeeee eeeeeeee eeee eeeee–eeeeeeeeeeeee eeeeeeeee 88 eee 88 ee eeeee ee eeeeeee eee eeee eeeeeeeeeeeeeeeeeeee.

Meeeee 88 Meeee–Meeeeeeeeeeee Meeeeeeee Meeeeeeeeeeeeeee Meeeeeeee ee 8-Meeeeeeeeee 8-Meeeeeeeeeeeeeeee eee 8-Meeeeeeeeee 8-Meeeeeeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) ee (%) Mee
Me 88 88 [‌88‌]
8-MM8M8 88 88 [‌88‌]
8-MeMM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-eeeeeee 88 88 [‌88‌]
Me 88 88 [‌88‌]

M8 Meeeeee Meeee (%) ee (%) Mee
8-MM8M8 MMMe8 88 88 [‌88‌]
8-MeM8M8 MMMe8 88 88 [‌88‌]
8-MeMM8M8 eeeeee/MMMe8 88 88 [‌88‌]
8-MeM8M8 eeeeee/MMMe8 88 88 [‌88‌]
8-eeeeeeee eeeeee/MMMe8 88 88 [‌88‌]
8-eeeeeee MMMe8 88 88 [‌88‌]

Meeeee MMMMM-eeeeeee eeeeeeeeee eeeee eee eeee eeeeeeeee eeeeeeeeeeee eeeeeeeeeeeeeee eee eee eeeeeeeeeeeeeeee ee eeeeeee.[‌88‌] Meeeeeeee ee eee-8-eeeeeeee eeee 8.8 eeeeeeeeeee ee M-eeeeeeeeeeeeeeee ee eee eeeeeeee ee 88 eee% ee eeeeeeee (M)-88 eeeeeee eee 8-eee eeeeeeee eeeeeeeee 88M eee 88M ee eeeeeeee ee eeeeeeeee eeeeee. Meeeeeeeeeeeeeeeeeee eee eeeeeeeee eeeeee ee eee eeee ee M-eeeeeee (88–88% ee) eeeeeeee ee M-eeeeeee (88–88% ee) (Meeeee 88). M eeeeeeeee eeeeeeeeee-eeeee eeeee eee eeeeeeee, eeee eeeeeeee eeeeeee eeeeeee eee Meøeeeee eeee eeeeeeee eeee ee 88 eee M-eeeeeeeeeeeeeeee, eee eeeeeee eee Meeee eeee eeeeee eeee ee 88 eee eee MM eeeeeeeeeeeee ee eee eeeeeeeee.

Meeeee 88 Meeeee Meeeeeeeee Meee Meeeeeeee Meeeeeeeeeeeeeee ee Meeeeee ­Mee-8-eeeeeeee[‌88‌]

Mee eeee eeee ee eeeeeeeeee eee eeeeeeee eee eee eeeeeeeeeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeeeeee ee eeeeeeeeeeeee. Meeeee, eeeeee eeeeeeeeee eeee (M)-88 eeeeeeeeeeee eeee­eeeee eee eeeeeeee ee M-eeeeeeeeeeeeeeee eeee eeeeeeeeeeeee 88, eeeeeeeeee eee eeeeeeeeeeeee eeeeeee eeeeeeeee eeeeeeee 88 eeeee eeeeeeeeeeeee ee eee eeeeeeeeeee eeeeee ee M-eeeeeeeeeeeeeeee (Meeeee 88).[‌88‌] Meeeeeeeeeeee, e eeeeeeee eeeeeeee ee eeeeeeeeeeeeeeeeee ee eeeeeeee eeee eeeee eee eeeeee eeeeeee eeee ee 88. Meee eeeeee eee eeeeeeeeeeee ee e eeeeee eeeeeeee eeeeeeeeee eeeee eeeee ee eeeee eeeeeeeee eeee M-eeeeeeeeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeeeeeeeee Meeeeeeeeeeeeeee ee Meeeeeeeeeeee Meeee e Meeeee Meeeeeeeee Meee ee Mee Meeeee Meeeeee Meee ee Meeeeeee[‌88‌]

Me eeeeeee eeeeeeeee ee Meeeeee 88.8.8.8.8.8, Meeee eeeee eeeeeeeeee eeeeeeee eeeee eeee eeee eeeee ee ee eeeeeeeee eeeeeeeee eee eeeeeeeeeeeeeeeee ee eeeeeee.[‌8‌] Meee eeeeeeee ee eeeeeeee eee eeeeeeee eeee ee eeeeeeeeee e eeeeeeee-eeeee eeeeee eeeeeeeeeeeeee eee eeeeeeeeee eeeeeeeeeeeeeeeeeeeee ee eeeeeee.[‌88‌] Meee, e eeeeee M8-eeeeeeeee eeeeeeee-eeeeeee eeeeeeee eeeeeeeeeeeeee eeeeeeee 88 eee eeeeeeee eee eeee ee eee eeeeeeeeeeeeeeee ee eeeeeeeeeeeeee eee-8-eeeeeeee, eeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeeeeee eeeeeeeeeeee 88 eeee ee ee 88% ee (Meeeee 88).

Meeeee 88 Meeeeeeeee Meeeeeeeeeeeeeeeeeeee ee Meeeeee Meeee e M8-Meeeeeeee Meeeeeee-Meeeeee Meeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) ee (%) Mee
Me Me 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
MM8MM=MM8 Me 88 88 [‌88‌]
Me Me 88 88 [‌88‌]
Me 8-MM8M8 88 88 [‌88‌]
Me 8-MeM8M8 88 88 [‌88‌]
Me 8-Mee 88 88 [‌88‌]

Mee ee eee eeeeeeee ee eeeeeeeee eeeeeeeeee eeeeeeeeeeeeeeee eeeeeeeee eeeeeeeee eeeee eeeeeee eee eee ee eeeeeeeeeeeeeee. Meeeeee, eeeee-eeeee Meeee eeee eeeeeeeee eeee eeee eeee eeeeeeeeeeee eeee ee eeeeeeee eeeeeeeeeeeeeeee eeeeeeeee. Mee eeeeeee, eeeeeeeee ee eeeeeee eeeeeeeee 88 eeee M-eeeeeeeeeeeeeeee ee eee eeeeeeee ee 8.88 eee% ee eeeeeeee(MMM) eeeeeeeeeeeeeeeeeeeeeeeee eee 8.88 eee% ee eeeeee M,M′-eeeeeee eeeeee 88 eeeeeee eee eeeeeee α-eeeee-β-eeeee eeeeeee 88 ee e eeeee-, eeeeeeeee-, eee eeeeeeeeeeeeeeee eeeeee eeee eeeeeeeee eeeeee (ee ee 88% eeeee, 88% ee, ee 88:8) (Meeeee 88).[‌88‌] M eeeeeeeeee eeeee eee eeee eeeeeeee ee eeeeeee eee eee eeeeeeee eeeee ee eeeeeeeeee eeeeeeeee, eeeee eeeeeeee(MMM) eeeeeeeeeee eeee eeee M-eeeeeeeeeeeeeeee eee eeeeeeee 88 (Meeeee 88).

Meeeee 88 Meeeeeee(MMM) Meeeeeeeeeeeeeeeeeeeeeeee Meeeeeeee Meeeeeeeeeeeeeee Meeeeeeeeeeeeeee ee α,β-Meeeeeeeeee Meeeeee[‌88‌]

Meee eeeeeeee, eee eeeeeeeeeeeeeeee eeeeeeeeeeeeeeee ee eeeeeeeee eee eeeeeeeeeee eeeeeeeee eeeee ee eeee(MMM) eeeeeee eeee e eeeeeeee eeeeeeee eeeeee M,M′-eeeeeee eeeeee 88. Meeeeeeeeee, eeee eeeeee eeeeeee ee eeee eeeeeeeee eee eeeeeeeeeeeeeeee ee eeeee eeeeeeeeee eeee ee eeeeeeee-eeeeeee eeeeeee.[‌88‌] Me eeee eeeeee, eee eeeeeeee eee eeeeeee eee eeeee ee M,M-eeeeeee-8-eeeeeeeeeeeeeeeeee/8-eeeeeeeeeeeeeeeeee eeeeeee ee eee eeeeeeeeeeeee eeeeeee eeeeee, eee eeeee ee eee eeeeeeeeeeeee eeeeeeee eeeeeeeeeee 88, ee eeee eeeeee eee eeee eeeeeeeee eeeeeeeeeeee eeeeeeee (88–88% ee) (Meeeee 88).[‌88‌]

Meeeee 88 Meeeeeeeeeeeeeee Meeeeeeeeeeeeeee ee Meeeeeee Meeeeeeeeee eee Meeeeeee-Meeeeee Meeeeee Meeee e Meeeee Meee(MMM)–M,M′-Meeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

Me8 Me8 Meeee (%) ee (%) Mee
Me Me 88 88 [‌88‌]
Me 8-MeMM8M8 88 88 [‌88‌]
Me 8,8-Me8M8M8 88 88 [‌88‌]
8-Mee Me 88 88 [‌88‌]
8-M8MM8M8 Me 88 88 [‌88‌]
8-M8MM8M8 Me 88 88 [‌88‌]

M8 M8 M8 Meeee (%) ee (%) Mee
M M Me 88 88 [‌88‌]
M M Me 88 88 [‌88‌]
M Me Me 88 88 [‌88‌]
M M 8-MeMM8M8 88 88 [‌88‌]
M M 8-eeeeeeee 88 88 [‌88‌]

Meee eeeee-eeeee eeeeeeee eee eeee eeeeeeeee ee eeeeeee eeeeeeeeeeeeee eeeeeeeeeeeeeeee eeeeeeeee. Me eeeee ee Meeeee 88, eeeeeeeee ee eeeee M-eeeeeeeeeeeeeee 88 eeee 8.8 eeeeeeeeeee ee M-eeeeeeeeeeeeeeee ee eee eeeeeeee ee e eeeeeeeee eeeeee ee eeeeeeee(MMM) eeeeeeeeeeeeeeeeeeeeeeeee eee eeeeee eeeeeeeee eeeeee 88 eeeeeee eee eeeeeeee eeeeeeeeeeeeee eeee eeeeeeeee eeeeeeeeeeeeeeeeeeee.[‌88‌] Meeeeeeeee, eee eeeeeeee eeeeeeee eeee eeeeeeee eeeeeeeeeeeeeeee ee eeee ee eee 8-eee eeeeeee, eeeeee ee eee eeee ee ee (M)-eeeeeeeeeee eeeeee eeeeeeeee 88, eeeee eeeee e eeeeeee ee 8-eee eee 8-eeee eeeeeeee eeee 8 eee 88% ee, eeeeeeeeeeee.

Meeeee 88 Meeeeeee(MMM) Meeeeeeeeeeeeeeeeeeeeeeee Meeeeeeee Meeeeeeeeeeeee Meeeeeeeeeeeeeee ee Meeee M-Meeeeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 Meeee (%) ee (%) Mee
Me M 88 88 [‌88‌]
Me M 88 88 [‌88‌]
MM8MMe M 88 88 [‌88‌]
(MM8)8MMe M 88 88 [‌88‌]
(MM8)8MMMee M 88 88 [‌88‌]
(M)-(MM8)8MM=MMMM8Me M 88 88 [‌88‌]
Me Me 88 88 [‌88‌]

M eeeeeeeee eeeeeeee eee eeee eeeeeeeeeeee eeeeeeeee eeeeeeee. Meeeee eee eeeeeeee eeeeeeeee eeeee, eeeee eee eeeee ee eeeeeeeeeeeee eeeeeeeeeeeeeeee, eeee eeeeee-eeeeeeeee eeeeeeee eeeeee ee e eeeeeee-eeeee eeee eeeeeeee. Meee, ee eee eeeeeeee ee e eeeeee(MM)–(M,M)-Me-MMM eeeeeee (MMM = eee-8,8-eeeeeeeeeeeeee), M-eeeee-eeeeeeeee 8-eeeeeeeeeeee (88) eeeeeeeee ee eeeeeeeeeeeeeeee eee-eeeeeeeeeeeeee eeeeeeee, eeeee eeeeeeeee e eeeeeee eeeeee eeeeeee eeeee eeeeeeeee ee eee M—Me(MM) eeee. Meeeeeeeee eeeeeee eeeeeeee eeee (8,8-eeeeeee-8-eeeeeeeeeeeeeeeee)eeeeeee eeeeeee eee eeeeeeeeee eeeeeeeeeeeee 88 ee 88% eeeee, eeee 88% ee (Meeeee 88).[‌88‌]

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeeeeeeeee Meeeeee Meeeeeeeeeeeeeee ee M-Meeee-Meeeeeeee 8-Meeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

(8M,8M)-8-[8-(Meeeeeeee)-8-eeeeeeeeee]eeeeeeeeeee-8,8-eeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeeeeee eeee ee eeeeeeeeeeee 88 (8.8 eeee) eee eee eeeeee Me eeee ee eeeeeeeeee eeee (M)-88 (8.888 eeee) ee eee eeeeeee (8 eM) eeeee eeeee eee eeeee MMM (8.8 eeee). Mee eeeeeee eee eeeeeee eee 88 e ee ee, eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeeee/MeMMe 8:8 ee 8:8).

8-(8-Meeeeeeeee)-8-[(8-eeeeeeeeeee)eeeeeeee]eeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me e eeee ee eee eeeeeeeeeee (8.88 eeee) eee eeeeeeee 88 (8.888 eeee) ee MM8Me8 (8.8 eM) eee eeeeeee (8.8 eM) ee −88 °M eeeee M8 eee eeeee M-eeeeeeeeeeeeeeee (8.888 eeee) ee eee eeee. Mee eeeeeeee eee eeeeeee ee −88 °M eee 8 e. Mee eeeeeee eee eeee eeeeeeee eeee eee. ee Me8MM8 (8 eM) ee −88 °M eee eeeeee ee 88 °M. Meeee eeeeeeee eeee M8M eee eeeeeeeeee eeee MM8Me8 (8 × 8 eM), eee eeeeeeee eeeeeee eeeeee eeee eeeeee eeee eeeee (8 eM), eeeee (Me8MM8), eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee.

M-{(M)-8-[(M)-8-Meeeee-8-eeeee-8-eee-8,8-eeeeeeeeeeee-8-ee]-8-eee-8-eeeeeeeeeee}-8-eeee­eeeeeeeeeeeeee (88, M8 = M8 = M; M8 = Me); Meeeeee Meeeeeeee:[‌88‌]

M eeee ee MeMMe8 (8.88 eeee) eee MeMM8 (8.88 eeee) ee MM8Me8 eeee 8-Å eeeeeeeee eeeeee (88 ee) eee eeeeeee ee 88 °M eee 8 eee. Meee, e 8.88 M eeee ee eeeeeeee Me(eeee)888 ee MM8Me8 (888 μM) eee eeeee. Meeee eeeeeeee eee 88 eee, eee eeeeeee eee eeeeee ee 88 °M, eee (M)-8-eeeeee-8-(8-eee-8-eeeeeeeeeeeeeeee)-8,8-eeeeeeeeeeee-8-eee (8.8 eeee) eee eeeee. Mee eeeeeeee eee eeeeeee eee 8 e. Mee eeeeeee (eeeeeeeee eeeeeeeeeeeee ee eee eeeeeee) eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeeeeee eeeee/MeMMe 8.8:8) ee eeeeee e eeeee eeeee; eeeee: 88%; [α]M88 +888.8 (e 8.88, MM8Me8).

References