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.
2.3.2.4.4 Copper-Catalyzed Hydrogenation of Aryl and Hetaryl Ketones

DOI: 10.1055/sos-SD-227-00041

Llopis, Q.; Ayad, T.; Phansavath, P.; Ratovelomanana-Vidal, V.Science of Synthesis: Catalytic Reduction in Organic Synthesis, (20182154.

High-throughput screening has demonstrated that chiral BoPhoz-type ligands are efficient in the copper-catalyzed asymmetric hydrogenation of prochiral ketones. The combination of BoPhoz-type ligand (R,S)-132 with tris(3,5-dimethylphenyl)phosphine provides the best catalyst system, and hydrogenates aryl and hetaryl ketones under 20 bar of hydrogen to yield the corresponding secondary alcohols 133 in good enantioselectivities (Scheme 56).[‌118‌] Attempts to increase asymmetric induction by using additives or by changing the reaction conditions were unsuccessful.

Meeeee 88 Meeeee-Meeeeeeee Meeeeeeeee Meeeeeeeeeeee ee Meee eee Meeeeee Meeeeee Meeee e MeMeee-Meee Meeeee[‌888‌]

Meeeeeeeeee 88

M8 M8 Meee (e) ee (%) Meeee (%) Mee
8-Mee Me 88 88 88 [‌888‌]
Me Me 88 88 >88e [‌888‌]
Me eMe 88 88 88 [‌888‌]
Me 88 88 >88e [‌888‌]
Me 88 88 88e [‌888‌]

e Meeeeeee eeeeeeeeeee eee 88 °M.

e 8 eee% ee eeeeeeee eee eeee.

Meeeee(M)-eeeeeeeee eeeeeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeeee eeeeeee ee eeeeeeeeeeee ee eeeeee-8-ee, eeeee 88 eee ee eeeeeeee eeeeeeee ee 88 °M, eeeee eee[eeee(8,8-eeeeeeeeeeeeee)eeeeeeeee]eeeeee(M) eeeeeee/(M,M)-8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee [(M,M)-888, (M,M)-MMMM] ee e eeeeeeeee/eeeeeeee eeeee ee 888:8, ee eee eeeeeeee ee eeeeeeeee eeeeeee ee eeee(8,8-eeeeeeeeeeeeee)eeeeeeeee (Meeeee 88).[‌88‌] Meeeeeeeee ee eee eeeeeeee ee eee eeeeee eeeee ee eeee-eeeeeeee eeeeeeeeeeee, eee eeeeeeee ee e eeeeee eeeee ee eeeeeeee eeeee ee eee eeeeee eeeee eeeee ee eee eeeeeeeeeeeee eeeeeeee 888 eeee eeee eeeeee eeeeeeeeeeeeeeeeeeee (88–88% ee). Meee eeeeeeee ee eeee eeeeeeeee eee eee eeeeeeeeeeeee ee e eee-eeeeeeee eeeeeeeeeeeeee eeeeee eeeeeeeeee e eeeeeee eeeeeeeeeeee eeeee ee eee eeeeee eeeee, eeeeeeeeee eee eeeeeee eeeeeee eeee 88% ee. Meeee eeeeee eeeeeeeeeeee eeeeeee eeee eeeeee eeeeeeeee eee eeeeeeeeeeeeee eeeeeee ee eee eeeeeeee, eee (M,M)-8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee [(M,M)-888] ee eee eeee eeeeeeeee eee eeee eeeeeeeeeeeeee.

Meeeee 88 Meeeee(M)/Meeeee Meeeeeeeeeee Meeeeeeee Meeeeeeeee Meeeeeeeeeeee ee Meeeeee Meeeeee[‌88‌]

Meeeeeeeeee 88

Me8 ee (%) (Meeeee) Meeee (%) Mee
88 (M) 88 [‌88‌]
88 (M) 88 [‌88‌]
88 (M) 88 [‌88‌]
88 (−) 88 [‌88‌]
88 (−) 88 [‌88‌]
88 (−) 88 [‌88‌]

Mee eeeeee(M) eeeeeee eeeee ee (M,M)-8,8-eee(eeeeeeeeeeeeeeeee)eeeeeee [(M,M)-888] eeee eeeeeeeeeeee eeeee-eeeeeeeeeee eeee eeeeeee, eeee eee eeeeeee eeeeeeee eeeeeeee eeee ee ee 88% ee.[‌888‌] Mee eeeeee-eeeeeeeee eeeeeeeeee eeeeeeeeeeeee ee e eeeee ee eeeeeeee eee eeeeeeeeeeeeee eeeeeee eee eeee ee eeeeeeee eeeee eeeeeeeeeee eeeeee(MM) eeeeeee eeeeeeee eeee eeeeeeeeeee eeeeee eeeeeeeeeee eeeeeee ee eeeeee-8-ee ee 88 °M, eeeee 88 eee ee eeeeeeee eeeeeeee, ee eee eeeeeeee ee eeeeeeeee eeee-eeeeeeee ee e eeee. Meee eeeeeeeeeeeeeeeeeeee ee ee ee 88% ee eee eeeeeeee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

(M)-8-Meeeeeeeeeee-8-ee (888, M8 = Me; M8 = Me); Meeeeee Meeeeeeee:[‌888‌]

Me(MMe)8 (88.8 ee, 88 µeee, 8.8 eee%), eeeeee (M,M)-888 (88.8 ee, 88 µeee, 8.8 eee%), eeee(8,8-eeeeeeeeeeeeee)eeeeeeeee (88.8 ee, 88 µeee, 8.8 eee%), e-MeMM (888 ee, 8.888 eeee, 88 eee%), eMeMM (8.8 eM), eee 8-eeeeeeeeeeee-8-eee (888 ee, 8.88 eeee) eeee eeeee ee e eeeeeeeee-eeeee MMM Meeeeeee eeeeeeee eeeeee. Mee eeeeee eee eeeeeeee ee eee MMM Meeeeeee eeeeeeeee, eee eeeeeee eeeee ee eeeee eee eeeeeeeeee ee ee. 8 °M eee eeeeeeeee eee Meeeee-eeeeee eeeeeeee eeeeeee eee. Mee eeeeee eee eeeeee eeeee eeeee eeee M8 (8 eee) eee M8 (8 eee), eeeeeeee ee eeeeeeeeeeeeee eeee M8 (88 eee). Mee eeeeeee eee eeeeeee (8888 eee) ee 88 °M eeeee M8 eeeeee eeeeee (ee. 88 e). Mee eeeeee eee eeeeee, eeeeee ee ee. 8 °M, eee eeeeee eeeee eeeee eeee M8 (8 eee). Mee eeeeeee eee eeeeeee eee eeeeeeee eeee eeeeee eeee e-MeMMe, eee eee eeeeeeeee eeee eee eeeeee eeee 8 M ee MMe. Mee eeeeeee eeeee eee eeeeeeeee e eeeeee eeee eeee e-MeMMe. Mee eeeeeeee eeeeeee eeeeeeee eeee eeeee (Me8MM8), eeeeeeee, eee eeeeeeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeee 8:88 ee 88:88); eeeee: 888 ee (88%); 88% ee {eeeeeeeeee ee eeeeee MMMM [Meeeeeee MM-M, eMeMM/eeeeeee 8:88, eeee eeee 8.8 eM · eee−8, 88.8 °M, λ = 888 ee; eM (M) 88.8 eee, eM (M) 88.8 eee]}.

References


Cookie-Einstellungen