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.
1.4.8.2 Hydrohetarylation of Alkenes

DOI: 10.1055/sos-SD-223-00229

Nakao, Y.Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis, (20161428.

Some heteroaromatic compounds are alkylated under nickel–NHC catalysis through insertion of alkenes into C—H bonds of the hetarenes. Indoles undergo the hydrohetarylation reaction exclusively at the C2-position under nickel–NHC catalysis (Scheme 5).[‌3‌] The reaction of 1-methylpyrrole takes place both at the C2- and C5-positions under similar reaction conditions to give a mixture of hydroarylation products (Scheme 6). Benzofurans (Scheme 7) and furans (Scheme 8) are also competent hetarene substrates and undergo C2 and linear-selective alkylation. A number of functional groups are tolerated, giving a variety of linearly alkylated heteroaromatic products.

Meeeee 8 Meeeeeeeeeeeee ee Mee-8-eeee Meeee Meeeeee Meeeeeeee ee Meeeee–MMM Meeeeeeee[‌8‌]

Meeeeeeeeee 8

M8 M8 M8 M8 Meeeeeee
(eee%)
Meeeeeeeee Meeee
(Meeeee/Meeeeeee)
Meeee
(%)
Mee
MM8Me M M (MM8)88Me Me(eee)8/8 (88) eeee, 8 e 88:8 88 [‌8‌]
M MM8Me M (MM8)88Me Me(eee)8/8 (8) eeee, 88 e 88:8 88 [‌8‌]
M Me M (MM8)8Me Me(eee)8/8 (88) eeeeeee, 88 e 88:8 88 [‌8‌]
M MMe M (MM8)88Me 8 (8) eeee, 88 e 88:8 88 [‌8‌]
M M(Me)Me M (MM8)8Me Me(eee)8/8 (88) eeeeeee, 88 e 88:8 88 [‌8‌]
M M M (MM8)88Me 8 (8) eeee, 88 e 88:8 88 [‌8‌]
M M (MM8)8Me Me(eee)8/8 (88) MeMe-Me (8.8 eeeee), eeeeeee, 88 e 88:8 88 [‌8‌]
M Me(MMe)8 M (MM8)8Me Me(eee)8/8 (88) eeeeeee, 88 e 88:8 88e [‌8‌]
M M MM8Me (MM8)88Me Me(eee)8/8 (88) eeee, 8 e 88:8 88 [‌8‌]
M M M MM8MM(MMe)8 Me(eee)8/8 (88) MeMe-Me (8.8 eeeee), eeee 88 e 88:8 88 [‌8‌]
M M M MMe8MM8MM8Me Me(eee)8/8 (88) eeee, 88 e 88:8 88 [‌8‌]
M M M MM8MeMe8Me Me(eee)8/8 (88) eeee, 88 e 88:8 88 [‌8‌]
M M M Me(eee)8/8 (88) eeee, 8 e >88:8 88 [‌8‌]
M M M Me-Me 8 (8) eeee, 88 e >88:8 88 [‌8‌]
M M M MeMe8 Me(eee)8/8 (88) eeee, 88 e >88:8 88 [‌8‌]

e 8% ee eeeeeeeee, eeeeeeeeeee eeeeeee eee 88% ee eeeeeeee-eeeeeeeee eeeeeee [M8 = Me(MMe)8–e(Me-Me)e] eeee eeee eeeeeeee.

Meeeee 8 Meeeeeeeeeeeee ee Mee-8-eee Meeee 8-Meeeeeeeeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee[‌8‌]

Meeeee 8 Meeeeeeeeeeeee ee Mee-8-eeee Meeee Meeeeeeeeee Meeeeeeee ee Meeeee–MMM Meeeeeeee[‌8‌]

Meeeeeeeeee 8

M8 M8 M8 Meeeeeee
(eee%)
Meeeeeeeee Meeee
(Meeeee/Meeeeeee)
Meeee
(%)
Mee
M M (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeee, 8 e 88:8 88 [‌8‌]
MM8Me M (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeeeeee, 88 e 88:8 88 [‌8‌]
Me M (MM8)8Me Me(eee)8/8 (8) eeeeeee, 88 e 88:8 88 [‌8‌]
MMe M (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeee, 88 e 88:8 88 [‌8‌]
M M (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeee, 88 e 88:8 88 [‌8‌]
M (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeee, 88 e 88:8 88 [‌8‌]
MeMe(MMeMe8)8 M (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeee, 88 e 88:8 88 [‌8‌]
M MMe (MM8)8Me Me(eee)8/8 (8) MeMe-Me (8.8 eeeee), eeee, 88 e 88:8 88e [‌8‌]
M M e-Me 8 (8) eeee, 88 e 88:8 88 [‌8‌]

e Meeeeeee eee ee 88 °M.

Meeeee 8 Meeeeeeeeeeeee ee Mee-8-eeee Meeee Meeeee Meeeeeeee ee e Meeeee–MMM Meeeeee[‌8‌]

Meeeeeeeeee 8

M8 M8 Meeeeeeeee Meeee (Meeeee/Meeeeeee) Meeee (%) Mee
M (MM8)8Me MeMe-Me (8.8 eeeee), eeee, 88 e 8:8 88e [‌8‌]
Me (MM8)8Me eeee, 88 e 8:8 88e [‌8‌]
Me e-Me eeee, 88 e >88:8 88e [‌8‌]
Me (MM8)8Me eeee, 88 e 88:8 88 [‌8‌]
MM8Me (MM8)8Me eeee, 88 e 88:8 88 [‌8‌]

e Mee 8,8-eeeeeeeeeeee eeeeeee eee eeee eeeeeeee ee 88% eeeee.

e 8 eee% eeeeeeee eee eeee.

Meeeee–MMM eeeeeeeee eeeeeeeeeeeeeeeee ee eeeeeeeeeee eeeeeeee eeee eeeeeeee eeeeeeeeeee ee eeee 8,8-eeeeeeeeeeee eeeeeeee (Meeeee 8).[‌8‌] Mee eeeeeeee eeeeeeeeeeeeeeee eeeeeeee ee eeeeeeeee eee-8-eeee eeeee eeee eee π-eeeeeeee eeeeeeeee ee eee eeee eeeee ee eeeeeeeeeee, eeeee eeeeeeeeeee eee M—M eeee eeeeeee eeeeeeeee eeeeeeeeeee eeeeeeeeeeee eeee e (8-eeeeeeeee)eeeeee(MM) eeeeeeeeeeee. Me eeeeeeee, eeeeeeeee ee eeeeeeeeeee eeeeeeeeeeee, eee eeeee eeeeeeeeeee ee eeeeeeeee eee-8-eeee eeeeeee eeee eeeeeeeee eeee eee ee eeeeee eeeeeeeee.[‌8‌] Mee eeeeeeee ee eeeeeeeeeeeeeeeee ee e Meeee eeee eeeeeeeeee, eeeeeee, eeeeeeee eee eeeeeeeeeee ee eeeee ee eee eeeeee eeeeeeee, ee eeee, eee eeeeeee, 8-(8-eeeeeeeee)eeeeeeeeeeeeee 88 ee eee eeeee eeeeeeee (Meeeee 88).[‌8‌] M eeeeeee eeeeeeeeee ee eeeeeeeeeeeeeeee ee eeeeeeeeeeeeeeeee eeeeeeeee ee eee eeeeeeee ee eeeeeee ee e Meeee eeee eeeeeeeeee ee eeee eeeeeeee ee eee eeeeeeeeeeeeeeeee ee eeeeeeeeeee (e.e., 8-eeeeeeeeee-8-eee), eeeee eee eeeeeee eeeeeeeeeee eeeeeeeeeeeee ee eeee 8-eeeeeeee-8-eeee eeeee eee eeeeeeee eeeeeeeeee (Meeeeee 88 eee 88).[‌8‌]

Meeeee 8 Meeeeeeeeeeeeeeee ee Meeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee[‌8‌]

Meeeeeeeeee 8

M M Meee (e) Meeee (%) Mee
M MM 8 88 [‌8‌]
MMe M 8 88 [‌8‌]
M M 8 88 [‌8‌]
M M 8 88 [‌8‌]

Meeeee 88 Meeeeeeeeeeeeeeee ee Meeeeeeeeee Meeee 8-Meeeeeeeeeeeeeeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee eee Meeeeeeeeeeeeeeee[‌8‌]

Meeeeeeeeee 88

Me8 Meee (e) Meeee (Meeeee/Meeeeeee) Meeeeee Meeee (%) Mee
Me 8 888:8 88 [‌8‌]
8-Mee 8 888:8 88 [‌8‌]
8-Mee 8 88:8 88 [‌8‌]
8-MeMM8M8 88 888:8 88 [‌8‌]
8-MM8M8 8 888:8 88 [‌8‌]

Meeeee 88 Meeeeeeeeeeeeeeee ee Meeeeeeeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee[‌8‌]

Meeeeeeeeee 88

M M Meeee (Meeeeeee/Meeeee) Meeeeee Meeee (%) Mee
MMe MM >88:8 88 [‌8‌]
MMe M 88:8 88 [‌8‌]
MMe M >88:8 88 [‌8‌]
8-MeMM8M8M M 88:8 88 [‌8‌]
M M 88:88 88 [‌8‌]

Meeeee 88 Meeeeeeeeeeeeeeee ee Meeeeeeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee eee Meeeeeeeeeeeeeeee[‌8‌]

Meeeeeeeeee 88

Me Meeee (Meeeee/Meeeeeee) Meeeeee Meeee (%) Mee
Me 88:8 88 [‌8‌]
8-Mee >88:8 88 [‌8‌]
8-Mee >88:8 88 [‌8‌]
8-MeMM8M8 >88:8 88 [‌8‌]
8-MM8M8 >88:8 88 [‌8‌]

Meeeeeeee eeeeeee eeeeeee eeeeeeeeeeeeeeeee eeeee eeeeeeee ee eeeeeeeeeee eeeeee–MMM eee Meeee eeee eeeeeeeee. Mee eeeee eeeeeeee Meeee eeee eeeeeeee 8 (MMM) ee eeeeeeeeeee eeee 8,8-eee(8,8-eeeeeeeeeeeeeeeee)eeeeeeee-8-eeeeeee (MMe) eeeee eeee eeee M8 eeeeeeeeeee (Meeeee 88).[‌8‌] M eeeeeee eeeeeeeeeeeeeeeee eeeeee eeeeeee eeeeeeee eeee eeeeeeee eeeeeeeeeee (Meeeee 88).

Meeeee 88 M8- eee Meeeee-Meeeeeeee Meeeeeeeee ee Meeeeeee eeee Meeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee eee ee Meeeeeee Meeee Meee[‌8‌]

Meeeeeeeeee 88

M8 Meee (e) Meeee (Meeeee/Meeeeeee) Meeee (%) Mee
(MM8)88Me 8 88:8 88 [‌8‌]
Me 8 >88:8 88 [‌8‌]
(MM8)8MM=MM8 88 88:8 88 [‌8‌]
(MM8)8MMMe-Me 88 88:88 88 [‌8‌]
88 >88:8 88 [‌8‌]
MeMe8 88 88:8 88 [‌8‌]

Meeeee 88 M8- eee Meeeeeee-Meeeeeeee Meeeeeeeee ee Meeeeeee eeee Meeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee eee ee Meeeeeee Meeee Meee[‌8‌]

Meeeeeeeeeeeeeeee eeeee eeeeeee[8,8-e]eeeeeeee eee eeee ee eeeeeeeee eeeeeeeeeeeee ee e eeeeee–MMM eeeeeee eee eeeeeeeeeeeeeeeee.[‌8‌] Mee eeeeeeeeeeeeeeeee eeeeeeee eeeeeeeeeee ee eee M8-eeeeeeee ee eee eeeeeeeeeeeeee eeee. Me eeeeeeeee eeeee, eee eeeeeeee eeeeeeee eeeeee eeeeeeeee eeeeeee eeeee eeeeee eeeeeeee (Meeeee 88), eeeeeee eeee eeeeee eeeeeeeeeee eeeee eeeeeeee eeeeeeeeee eeeeeeee (Meeeee 88).

Meeeee 88 M8- eee Meeeee-Meeeeeeee Meeeeeeeee ee Meeeeee[8,8-e]eeeeeeee eeee Mee-8-eee Meeeeeeee ee e Meeeee–MMM Meeeeee eee Meeeeeeeeeeeeeeee[‌8‌]

Meeeee 88 M8- eee Meeeeeee-Meeeeeeee Meeeeeeeee ee Meeeeee[8,8-e]eeeeeeee eeee Meeeeeeeeee Meeeeeeee ee e Meeeee–MMM Meeeeee eee Meeeeeeeeeeeeeeee[‌8‌]

Meeeeeeeeee 88

Me8 Meeee (%) Mee
8-Mee 88 [‌8‌]
8-Mee 88 [‌8‌]
8-Mee 88 [‌8‌]
8-MeMM8M8 88 [‌8‌]
8-MM8M8 88 [‌8‌]

M eeeeeee–MMM eeeeeeee eee eeee eeeee ee eeeeee M8- eee eeeeee-eeeeeeeee eeeeeeeeeeeeeeeee ee eee-8-eeee eeeee 8,8′-eeeeeeeeee (Meeeee 88).[‌88‌] Mee eeeeeeeeeeeeee eeeee eeeee ee eeee eee M8-eee M8′-eeeeeeeee ee eeee e eeeeeee ee eeeeeeeeeee 8,8′-eeeeeeeeee eeeeeeee.

Meeeee 88 Meeeeeeeeeeeeeeee ee Mee-8-eeee Meeee 8,8′-Meeeeeeeee Meeeeeeee ee e Meeeeee–MMM Meeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) Mee
Me 88 [‌88‌]
eMe 88 [‌88‌]
Me 88 [‌88‌]
e-Me 88 [‌88‌]
(MM8)8MMMMM 88 [‌88‌]
MeMe8 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

8-Meeee-8-eeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

Me e eeeeeee ee Me(eee)8 (8.8–88 µeee), MMeMe (8; 8.8–88 µeee), eee eeeeee 88 (8.88 eeee) ee e 8-eM eeee ee e eeeeee eee eeeee ee eeeeee 88. Mee eeee eee eeeeee eeee e eeeee eee, eeeee eeeeeee eee eeeeee, eee eeeeee ee 888 °M. Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee e eee ee eeeeee eee eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee-eeeeeeee eeeeeeeeeeeeee (eeeeee eee).

8-(8-Meeeeeeee)eeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

M eeee ee Me(eee)8 (88 ee, 88 µeee) eee MMee (88 ee, 88 µeee) ee eeeeee (8.8 eM) eee eeeee ee eeeeeeee 88 (8.8 eeee) ee e 8-eM eeee ee e eeeeee eeeeee eeeeeeee ee eeeeeee (8.8 eeee). Meeee eeeeeeee (eeeeeeee eeeeeeee; 88 ee, 8.88 eeee) eee eeeee, eee eeee eee eeeeee eeee e eeeee eee, eeeee eeeeeee eee eeeeee, eee eeeeee ee 888 °M. Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee e eee ee eeeeee eee eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

8-(8-Meeeeeeee)-8-eeeeeeeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

Me e eeee ee Me(eee)8 (88 ee, 88 µeee), eeeeeee 88 (88 ee, 88 µeee), eee 8-eeeeeeeeeeeeeeeeeee (8.88 eeee) ee eeeeeee ee e eeee eeee eeeee eee eeeeeeeeee 88 (8.88 eeee) eee Me8Me ee eeeeeee (8.88 eM, 88 µeee). Meeee eee eeee eee eeeeee eeee e eeeee eee, ee eee eeeee eeeeeee eee eeeeeeee eee eeeeee ee 888 °M. Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee Meeeee, eeeee eee eeeeee eeee MM8Me8. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeee eeeeeee, eeeee eee eeeeeee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

8-(8-Meeeeeeeee)eeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

Me e eeee ee Me(eee)8 (88 ee, 88 µeee), MMee (88 ee, 88 µeee), eee eeeeeeee 88 (8.88 eeee) ee eeeeeee eee eeeee eeeeeeeeeeee (8.8 eeee). Meeee eee eeee eee eeeeee eeee e eeeee eee, ee eee eeeee eeeeeee eee eeeeeeee eee eeeeee ee 888 °M eee 88 e. Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee Meeeee, eeeee eee eeeeee eeee MM8Me8. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeee eeeeeee, eeeee eee eeeeeee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

8-(8-Meeeeeeeee)-8-eeeeeeeeeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

Me e eeee ee Me(eee)8 (88 ee, 88 µeee), MMe (88 ee, 88 µeee), eee 8-eeeeeeeeeeeeeeeeeee (8.88 eeee) ee eeeeeee ee e eeee eeee eeeee eeeeee 88 (8.8 eeee) eee Me8Me ee eeeeeee (8.88 eM, 88 µeee). Meeee eee eeee eee eeeeee eeee e eeeee eee, ee eee eeeee eeeeeee eee eeeeeeee eee eeeeee ee 888 °M eee 88 e. Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee Meeeee, eeeee eee eeeeee eeee MM8Me8. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee ee eeeeee eee eeeee eeeeeee, eeeee eee eeeeeee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

8-Meeeeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

Me e eeeeeee ee eeeeeeee (8.8 eeee) eee Meeee eeee 8 (88 ee, 8.88 eeee) eeeeeeee ee e 8-eM eeee eee eeeee e eeee ee Me(eee)8 (88.8 ee, 88 µeee) eee MMe (88.8 ee, 88 µeee) ee eeeeeee (8.8 eM) ee e eeeeee. Meeee eeeeeeee ee eeeeee 88 (8.8 eeee) eee eeeeeeee (eeeeeeee eeeeeeee; 88 ee, 8.88 eeee), eee eeee eee eeeeee eeee e eeeee eee, eeeee eeeeeee eee eeeeee, eee eeeeee ee 888 °M. Mee eeeeeeeee eeeeeee eee eeeeeeee eeeeeee e eee ee eeeeee eee eee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee-eeeeeeee eeeeeeeeeeeeee (eeeeee eee).

8-(8-Meeeeeeee)eeeeeee[8,8-e]eeeeeeeee 88; Meeeeee Meeeeeeee:[‌8‌]

MMMMMMM: Meee eeeeeeeeeeeeeeeee ee eeeeee eeeeeeeeee.

Me e eeeeeeee, e 88-eM eeee eee eeeeeee eeee Me(eee)8 (8.8 ee, 88 µeee), MMee (88 ee, 8.88 eeee), eee eeeeeee[8,8-e]eeeeeeee (8.88 eeee) ee eee eeeeeee (8 eM), eee eee eeeeeee eee eeeeeee eee 8 eee, eeeeeeee ee eeeeeeee ee 8.8 M Me8Me ee eeeeeee (8.8 eM, 8.88 eeee). Meeee eeeeeeee eee 8 eee, eeeeee 88 (8.88 eeee) eee eeeee. Mee eeee eee eeeeee eeee e eeeee eee eee eeeee eeeeeee eee eeeeeeee. Meeee 88 e ee eeeeeee ee 888 °M, eee eeeeeee eee eeeee ee MM8Me8, eeeeeee eeeee eee eee 88 eee, eee eeeeeeee eeeeeee e Meeeee eee. Mee eeeeeeee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee).

8,8′-Meeeeee-8,8′-eeeeeeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

Me ee eeee-eeeee, eeeee-eeeeee eeee eeee eeeee 8,8′-eeeeeeeeee (8.88 eeee), MMee•MMe (8.8 ee, 8.8 µeee), Me(eeee)8 (8.8 ee, 8.8 µeee), MeMe-Me (8.8 ee, 88 µeee), eee eeeeeee (8.8 eM). Meeeee 88 (8.8 eeee) eee eeeee ee eee eeeeeee, eeeee eee eeee eeeeeeeeee eeeeeee ee 888 °M. Mee eeee eee eeeeee ee ee eee eee eeeeeee eee eeeeeee eeee MeMMe. Mee eeeee eeeeeee eee eeeeeeee eeeeeee e eee ee eeeeee eee, eee eeeeeee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).

References