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.
1.1.16.1.2.2 Using Chiral Thioureas as Brønsted Acid Activators with Achiral Amine Nucleophiles

DOI: 10.1055/sos-SD-204-00330

Hatakeyama, S.Science of Synthesis: Asymmetric Organocatalysis, (20121682.

A dual catalytic system of an achiral amine nucleophile and a chiral thiourea activator enantioselectively promotes the reactions of aliphatic and aromatic aldehydes with cyclohex-2-enone to give the corresponding MoritaBaylisHillman products (e.g., 30, 32, 34 and 36) in moderate to good yields; the catalyst systems 4-(dimethylamino)pyridinethiourea 29 (Scheme 10),[‌33‌] 1,4-diazabicyclo[2.2.2]octanethiourea 31 (Scheme 11),[‌34‌] triethylaminethiourea 33 (Scheme 12),[‌35‌] and 1,4-diazabicyclo[2.2.2]octanethiourea 35 (Scheme 13)[‌36‌] are effective promoters for these transformations.

Meeeee 88 Meeeeeeee ee Meeeeeeee eeee Meeeeeee-8-eeeee Meeee 8-(Meeeeeeeeeeee)eeeeeeee eee e Meeeeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) eee (%) Mee
Me 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
(MM8)8Me 88 88 [‌88‌]
(MM8)8Me 88 88 [‌88‌]
eMe 88 88 [‌88‌]
88 88 [‌88‌]
Me 88 88 [‌88‌]

e Meeeeeeeee ee MMMM ee e eeeeee eeeeeeeeee eeeee.

Meeeee 88 Meeeeeeee ee Meeeeeeee eeee Meeeeeee-8-eeeee Meeee 8,8-Meeeeeeeeeee[8.8.8]eeeeee eee e Meeeeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) eee (%) Mee
Me 88 88 [‌88‌]
Me 888e 88e [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
8-MeMM8M8 88 88 [‌88‌]
(MM8)8Me 88 88 [‌88‌]

e Meeeeeeeee ee MMMM ee e eeeeee eeeeeeeeee eeeee eeeeee eeeeeeeee eeeee.

e MM eeeee.

e Meeeeeeeee ee MM ee e eeeeee eeeeeeeeee eeeee.

Meeeee 88 Meeeeeeee ee Meeeeeeee eeee Meeeeeee-8-eeeee Meeee Meeeeeeeeeeee eee e Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meee (e) Meeee (%) eee (%) Mee
Me 888 88e 88 [‌88‌]
888 88e 88 [‌88‌]
eMe 888 88 88 [‌88‌]
(MM8)8Me 888 88 88 [‌88‌]
(M)-MM=MMMe 888 88 88 [‌88‌]
Me 888 88e 88 [‌88‌]
8-MeM8M8 888 88 88e [‌88‌]
8-MeMM8M8 888 88 88 [‌88‌]

e Meeeeeeeee ee MMMM ee e eeeeee eeeeeeeeee eeeee.

e Mee eeeeeeee eee eeeeeee eee ee 8°M eeeee 88 (88eee%) eee Me8M (88eee%).

e Mee eeeeeeee eeeeeeeeeeeee eee eee eeeeeeeeee.

Meeeee 88 Meeeeeeee ee Meeeeeeee eeee Meeeeeee-8-eeeee Meeee 8,8-Meeeeeeeeeee[8.8.8]eeeeee eee e Meeeeeeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (%) eee (%) Mee
8-M8MM8M8 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8,8-Me8M8M8 88 88 [‌88‌]
8,8-Me8M8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MeM8M8 88 88 [‌88‌]
8-MM8M8 88 88 [‌88‌]
8-MM8M8 88 88 [‌88‌]
8-M8MM8M8 88 88 [‌88‌]
Me 88 88 [‌88‌]
8-eeeeeee 88 88 [‌88‌]
8-Mee 88 88 [‌88‌]
8-MeM8M8 88e 88 [‌88‌]

e Meeeeeeeee ee MMMM ee e eeeeee eeeeeeeeee eeeee.

e Mee eeeeeeee eee eeeeeee eee eee 88e.

Meeeeeeeeeee Meeeeeeee

(M)-8-[Meeeeeeeee(eeeeeee)eeeeee]eeeeeeee-8-ee-8-eee (88, M8=Me); Meeeeee Meeeeeeee:[‌88‌]

Meeeeeeeeeeeeeeeeeeeeee (88µM, 8.88eeee) eee eeeee ee e eeeeeee ee eeeeeeee-8-eeeee (888µM, 8.88eeee), eee eeeeeeeeeee eeeeeeee 88 (888ee, 8.88eeee), eee MMMM (88.8ee, 8.88eeee) eeee ee 8°M. Mee eeeeeeeee eeeeeee eee eeeeeee eeeeeeeeee ee 8°M eee 88e, eeee eee. ee MM8Me eee eeeee, eee eee eeeeeee eeeee eee eeeeeeeee eeee MeMMe. Mee eeeeeeee eeee eeeee (MeMM8), eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 8:8 ee 8:8) ee eeee eee eeeee eeeeeeee; eeeee: 888ee (88%); 88% ee.

(M)-8-(Meeeeeeeeeeee)eeeeeeee-8-ee-8-eeee 88; Meeeeee Meeeeeeee:[‌88‌]

MMMMM (8.88ee, 88.8µeee) eee eee eeeeeeeeeee eeeeeeee 88 (88.8ee, 88.8µeee) eeee eeeeeeeee ee eeeeeeee-8-eeeee (88µM, 8.88eeee), eee eeeeeeeee (88µM, 88.8µeee) eee eeeee ee eeeeeeee eeeeeeee. Mee eeeeeee eee eeeeee ee 88°M ee e eeeeeeee eeeeee eeeee eee eee eeeeeeee (888µeee) eee eeeee. Mee eeeeeee eee eeeeee ee 88°M eee eeeeeee ee 888 eee. Meeeeeee ee 88.8µM eeee eeeee ee eeeeeeeee eee eeeeeeee ee MM ee e eeeeee eeeeeeeeee eeeee. Meeeeee, eeee MMMM eeeeeeee eee eeeeeeee eee eeeeeeee eee eeeeeee eeeee 88e, eee eee eeeeeee eee eeee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee).

(M)-8-(Meeeeeeeeeeee)eeeeeeee-8-ee-8-eeee 88; Meeeeee Meeeeeeee:[‌88‌]

Meeeeeee-8-eeeee (88µM, 8.8eeee) eee Me8M (8.8µM, 8.88eeee) eeee eeeee ee e eeeeee eeee eeeeeeeeee eee eeeeeeee eeeeeeee 88 (88.8ee, 8.88eeee). Mee eeeeeee eee eeeeeee eee 8eee, eee eeee eee eeeeeeee (8.8eeee) eee eeeee ee 8°M. Meeee 888888e ee 8°M, eee eeeeeee eee eeeeeeee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeeeee eeeee/Me8M 88:8 ee 88:88).

(M)-8-[Meee(eeeeeee)eeeeee]eeeeeeee-8-ee-8-eeee 88; Meeeeee Meeeeeeee:[‌88‌]

Meeeeee-8-ee-8-eee (88µM, 8.88eeee) eee eeeee ee e eeeeeee ee eee eeeeeeee (8.88eeee), MMMMM (8.88eeee), eee eee eeeeeeee eeeeeeee 88 (8.88eeee) ee eeeeeee eeeeeeeee eeeee ee eeeee eeeeeeeeee. Mee eeeeeee eee eeeeeee ee ee (eeeeeeeee eee 8e), eeeeee ee eee eeeeeeeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeeee eeeee).

References