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2.3.6.3.2 Relay Catalysis of Brønsted Acids with Transition-Metal Complexes

DOI: 10.1055/sos-SD-205-00523

Han, Z. -Y.; Wang, C.; Gong, L. -Z.Science of Synthesis: Asymmetric Organocatalysis, (20122721.

The first reported example of relay catalysis with combination of a transition-metal and a Brønsted acid is a binary catalyst system consisting of a ruthenium hydride complex and a Brønsted acid which enables a one-pot tandem alkene isomerization/FriedelCrafts reaction (Scheme 32).[‌61‌] In this relay catalytic reaction, the allyl amide 63 isomerizes to enamide 65 catalyzed by 1mol% of carbonylhydridotris(triphenylphosphine)ruthenium(I) [RuH(CO)(PPh3)3]. Subsequently, the tautomerization of enamide to imine 66 takes place in the presence of Brønsted acid 64 and the resultant imine is activated by the Brønsted acid 64 to undergo a FriedelCrafts reaction with electron-rich arenes. However, an enantioselective version of the reaction is as yet unavailable.

Meeeee 88 Meeeee Meeeeeeeeeeee/MM Meee-Meeeeee Meeeeeee[‌88‌]

Me eeeeeeeeee eeeeeee eeeeee eeeeeeeeeeeee/eee-MeeeeeeMeeeeee eeeeeeee eee eeee eeeeeeee eeeee ee eeeeeeeeeeee eeeeeeeee ee e eeeeee eeeeeee eeeeeee eee e eeeeee Meøeeeee eeee (Meeeee 88).[‌88‌] Mee eeeeeeeeee eeeee eeeeee 88 eeeeeee eeeeee eeeeeeeee ee eee eeeeeeee ee eeeeee eeeeeee eeeeeeeee ee eeeeee M-eeeeeeeeee eeeee eeeeee 88. Meeeeeeeeeeeeee eeee-β-eeeeeeeeeeeeee 88 eee eeeeeeee eeee eeeeeeeeeeeee eeeeeeeee ee eee eeeeee Meøeeeee eeee 88, eeeee eee eeeeeeeeeeee eeeeeee ee eeee ee eeee β-eeeee eeeeeee eeeeeeee 88 ee eeeeeeeee eeeeeeeeeeeeeeeeeeee (ee ee 88% ee) (Meeeee 88). Meeeeee, eee eee eeeeeeeee eeeeeeee ee eee eeeeeeee eee eeeeeee eee eeeeeeeeee eeeeee eeee ee e eee-eeeeeeeee eeeeeeeee, eee eeee ee ee eee eeeeee eeeee eeeeeeeee.

Meeeee 88 Meeeeeeeee Meeeeeeeeeeeee ee Meeeeeeeee Meeee Meeeee ee Meeee Meeeeeee ee Meeeee-Meee Meeeeeeeeeeee/Meeeeeeeee Mee-MeeeeeeMeeeeee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 Meeee (M/M) ee 88 Meeeeeeeee ee (eeee/eee) ee (%) Meeee (%) Mee
Me 88:8 eeeeeee, 88°M, 8e 88:8 88 88 [‌88‌]
Me 88:8 MeMMe, 88°M, 8e 88:8 88 88 [‌88‌]
(MM8)8Me 88:8 eeeeeee, 88°M, 8e 88:8 88 88 [‌88‌]
eMe 88:8 MeMMe, 88°M, 8e 88:8 88 88 [‌88‌]
Me 88:8 MeMMe, 88°M, 8e 88:8 >88 88 [‌88‌]
Me 88:8 MeMMe, 88°M, 8e 88:8 88 88 [‌88‌]

M eeeeeee eeeeeeeee-eeeeeeeee eeeee eeeeeeeeee[‌88‌] ee eeeee eeeeee 88 (M=M) eeee eeeeee 88 eee Meøeeeee eeee eeeeeeeee eeeeeeeeeeeeee MeeeeeeMeeeee eeeeeeee eee eeee eeeeeeeeeee.[‌88‌] Mee eeeeeeeeeeee eeeeeee eeeee eee ee eeeeeeeee ee eeee eeee eee eeeeeeeeee eeeeeeee ee eeeeeee eeeeee 88 eee eeeee 88 ee eee eeeeeeee ee MeeeeeMeee eeeeeeee 88 eee eeeeeee eeeeeeeee ee eeeeeeeeeeeeee MeeeeeeMeeeee eeeeeeee eeeeeeeee ee eeeeee Meøeeeee eeee eee-88 ee eeeeee eeeeeeeeee eeeeeee 88 ee eeeeeeeee eeeeee eee eeeeeeeeeeeeeeeeeeee (Meeeee 88).

Meeeee 88 Meeee Meeeeeeeee/MeeeeeeMeeeee Meeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M M8 Meee (°M) ee (%) Meeee (%) Mee
M M M Me 88 88 88 [‌88‌]
M M M Me 88 88 88 [‌88‌]
M MMe M Me 88 88 88 [‌88‌]
Me M M Me 88 88 88 [‌88‌]
M Me M Me 88 88 88 [‌88‌]
M Me M Me 88 88 88 [‌88‌]
M M M Me 88 88 88 [‌88‌]
M M M Me 88 88 88 [‌88‌]
Me M M Me 88 88 88 [‌88‌]
M M M 8-MeM8M8 88 88 88 [‌88‌]
M M M 8-MeM8M8 88 88 88 [‌88‌]
M M M 8-Mee 88 88 88 [‌88‌]
M M M 8-MeMM8M8 88 88 88 [‌88‌]
M M M 8-M8MM8M8 88 88 88 [‌88‌]
M M M 8-eeeeeeee 88 88 88 [‌88‌]
M M M 8-eeeee 88 88 88 [‌88‌]
M M MMee Me 88 88 88 [‌88‌]

Meee eeeeeeee, eeee eeeeeeeee eeee eeeee eeeee eeeee ee eeeeeeeeee MM eeeee eeeeee eeeeeeeeeeee eeeeeeee,[‌88‌,‌88‌] eeee ee eeeeeeeeeeeeee.[‌88‌] Mee eeeeeeeeeeeee ee eeee eeeeeeeee eeee Meøeeeee eeeee eee eeee eeeeeeeeeeee eeeeeeeeeeee eeeeeeeeeeeee[‌88‌,‌88‌] ee eee eeeeeeeeeeeeee/eeeeeeee eeeeeeeeeeeee eeeeee eeeeeeee.

8-Meeeeeeeeeeeeeeee 88 eee eeeeeeee eeeeeeeeeee eeee eeeeeeeeeeeeeeeeeeee 88 eeee eeeeeeeee eeeeeeeeeeeeeeeeee eeeee eee eeeee eeeeeeeee ee ee eeeeeee eeee eeeeeee eee eeeeee eeeeeeeeee eeee 88 (Meeeee 88).[‌88‌] Mee eeeeeeee ee eeeeeeeeee ee ee e eeeeeeeeeee eeeeeeeee eeeeeee eeeeeeeeee ee e eeee-eeeeeeeee eeeeeeeeeeeeee eeeeeeeeeeeeee ee e MM eeee eee e Meøeeeee eeee eeeeeeeee eeeeeeeeeeeeeeee eeeeeeee eeeeeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeeeeeeee Meeeeeeeeeeeee/Meeeeeeeee Meeeeeee Meeeeeeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 ee (%) Meeee (%) Mee
Me M M 88 88 [‌88‌]
8-Mee M M 88 88 [‌88‌]
8-Mee M M 88 88 [‌88‌]
8-MeM8M8 M M >88 88 [‌88‌]
8-MM8M8 M M 88 >88 [‌88‌]
8-MeMM8M8 M M 88 >88 [‌88‌]
8-eeeeeeee M M 88 88 [‌88‌]
8-Mee M M 88 88 [‌88‌]
8-M8MM8M8 M M >88 88 [‌88‌]
Me M M 88 88 [‌88‌]
(MM8)8Me M M 88 88 [‌88‌]
Me MMM8M 88 88 [‌88‌]
Me Me M 88 >88 [‌88‌]
Me M M 88 88 [‌88‌]
Me Me M 88 >88 [‌88‌]
Me M Me 88 >88 [‌88‌]
Me (MM=MM)8 88 88 [‌88‌]

Meeeee 88 Meeee Meeeeeeee ee Meee Meeeeee/Meeeee Meøeeeee Meee Meeeee Meeeee ee Meeeeeeeeee Meeeeeeeeeeeee Meeeeeeeeeeeee/Meeeeeeeee Meeeeeee Meeeeeeeeeeee[‌88‌]

Me eeeeeeeeeeeeee eeeeeeeeeeeeee/eeeeeeee eeeeeeeeeeeee eeeeeee eee eeee eeeeeeeeeeee eeeeeeeeeee ee eee eeeeeeee eee ee ee eeeeeee eeee eeeeeee eee eeeeee eeeeeeeeee eeee eee-88 ee eeeeeeee eeeee eeeeeee eee eeeeeeeeee eeeeeeeeeeeeee/eeeeeeeee ee eeeeeee eee eeeeeeee ee eeee eeeeee 88 ee eeeeeeeee eeeeee eee eeeeeeeeeeeeeeeeeeee (Meeeee 88).[‌88‌] Me eee eeeeeeee ee eeee Meøeeeee eeee eee eeeeeeeeeeeeee eeee eee eeeeeee. Mee eeee eeeeeee ee eee eeee e eeee eeeeeeee ee eee eeeeeeeeeeeeee, eee ee ee eeee eeee ee eeeeeee eeeeeeee eeeeeeeeeeeee ee eeeeeeeeeeeee eeee eee Meøeeeee eeee. Meeeeeeeee, ee eee eeeeeeee ee eeee eeeeeee eeee eeeeeee eee eeeeee Meøeeeee eeee, eeee eeeeeeeeee eeeeeeee eeeeeeeeeeeee eeeeee eeeeeee eeeeeee ee eeeeeeeeeee.

Meeeee 88 Meeeeeeeeeeeee Meeeeeeeeeeeee/Meeeeeeeee Meeeeeee Meeeeeeeeeeee[‌88‌]

Me 8888, e eeeee-eeeeeeeee eeeeeee eeeeeeee eee eee eeeeeeeeeeeeeeee eeeeeeeeeeee ee eeeeeeeeeeee eeeeeee eeeeeeeeeeee eee eeee eeeeeeee.[‌88‌] Mee eeeeeeee eeeeeeeee eeee eeeeee Meøeeeee eeee eeeeeeeee Meeeeee eeeeeeee eeeeeee 8-eeeeeeeeeeeeeeeee 88, eeeeeeeee 88, eee eeeeee eeeeeeeeeeeeee (88) ee eeeee eeeeeeeeeeeeeeeeeeee 88, eeeee eee eeeeeeeeeeee eeeeeeeeeee ee eeeeeeeeee eeeeeeeeeee 88 eeeeeee e eeee-eeeeeeeee eeeeeeeeeeeeee. Mee eeeeeeeee ee 88 eeee eeeeee eeeeeeeeeeeeeeeeeeeee ee eee eeeeeeee ee eeeeee eeee eeeee eeeeeeeeee 88 ee eeee eeeeee eee eeeeeeeee eeeeeeeeeeeeeeeeeeee (Meeeee 88). Meeeeeeeeee, eeeeeeeeeee eeeeeee eeeeeeee eeee eee Meøeeeee eeee 88 ee eee eeee eeeeeeee eee eee Meeeeee eeeeeeee, eeeeeee eeeeeeeeeeeeee ee eeeeeeeee ee ee eeee eeeeeeeee eeee(M) eeeeeeeee 88 eeeeee eeee eeee eeeeeeee 88.

Meeeee 88 Meeeeeeee ee Meeeeeeeee Meeeeeeeeee ee Meeee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 M8 ee (%) Meeee (%) Mee
M M Me 8-MeM8M8 88 88 [‌88‌]
M M Me Me 88 88 [‌88‌]
M M Me 8-MeM8M8 88 88 [‌88‌]
M M Me 8-Mee 88 88 [‌88‌]
M M Me 8-MeMM8M8 88 88 [‌88‌]
M M Me 8-MMM8M8 88 88 [‌88‌]
M M Me 8-MeM8MM8M8 88 88 [‌88‌]
M M Me 8-M8MM8M8 88 88 [‌88‌]
M M Me 8-MeM8M8 88 88 [‌88‌]
M M Me 8-M8MM8M8 88 88 [‌88‌]
M M Me 8-M8MM8M8 88 88 [‌88‌]
M M Me 8-MeMM8M8 88 88 [‌88‌]
M M Me 8-eeeee 88 88 [‌88‌]
M M Me (MM8)8Me 88 88 [‌88‌]
M M 8-MM8M8 8-MeM8M8 88 88 [‌88‌]
M M 8-eeeeeeee 8-MeM8M8 88 88 [‌88‌]
Me M Me 8-MeM8M8 >88 88 [‌88‌]

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

Meeeee 88 Meeeeeeee ee Meeeeeeeee Meeeee Meeeeeeeeee ee Meeee Meeeeeeee[‌88‌]

Meeeeeeeeee 88

M8 M8 M8 ee (%) Meeee (%) Mee
Me M M 88 88 [‌88‌]
(MM8)8Me M M 88 88 [‌88‌]
(MM8)88Me M M 88 88 [‌88‌]
Me Me M 88 88 [‌88‌]
(MM8)8Me Me M 88 88 [‌88‌]
(MM8)88Me Me M 88 88 [‌88‌]
Me M Me 88 88 [‌88‌]
(MM8)8Me M Me 88 88 [‌88‌]
(MM8)88Me M Me 88 88 [‌88‌]

Meeeeeeeeeee Meeeeeeee

eeee-Meeee [(8M,8M)-8-Meeeeee-8-eeeeee-8-eeeeeeeeeee-8-ee]eeeeeeeee (88, M8=Me); Meeeeee Meeeeeeee:[‌88‌]

M 8.88M eeee ee MeMMMe8 ee MMM (88.8µM, 8.888eeee) eee eeeee ee e eeee ee [8,8-eee(ee-8-eeeeeeeeeeeeee)eeeeeeee]eeeeeeeeeeee(MM) [MeM8(8-Mee-MMMMMM); 88.8ee, 8.888eeee, 88eee%] ee MMM (8.88eM) eeeee eeeee. Meeee eee eeeeeee eee eeee eeeeeee ee 8°M eee 8eee, eeeeeee eeee-eeeee (8-eeeeeeee-8-eeeeeeeeeee)eeeeeeeee (88, M8=Me; 8.88eeee, 88.8ee) eee eeeee ee eee eeeeeee eee eeee eee eeeeeeeeee eee eeeeeeee eeee eeeee eeeee. Meeee eeeeeeee ee 8°M eee 88e, 88% ee M8M8 (8.8eM) eee eeeee eee eee eeeeeee eee eeeeeee ee ee eee 88eee. Mee eeeeeee eee eeeeeee eeee eee. ee Me8MM8 eee eeeeeeeee eeee MeMMe (8×). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8) eee eeeeeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeee eeee eeeeee eee Meeeeeee eee eeeee. Meeee eeeeeeeeee eeeeeee e eeeee eeeeee (eeeeee eee, eeeeee/MeMMe 8:8), eeee-eeeee [8-eeeeee-8-(eeee-8-ee-8-eeeee)eeeee]eeeeeeeee [88, M8=Me; eeeee (M/M) 88:8] eee eeeeeeee ee e eeeee eeeee. Meee eeeeeeee eee eeeeeeee eee eee eeeeeeeeee eee-MeeeeeeMeeeeee eeeeeeeeeeeee eeeeeee eeeeeee eeeeeeeeeeee. Meee, eee eeeeeee eee eeeeeeeeeee ee e eeeee eeee eeee. Mee eeeeeeeeee eee eeeeeeee eeee M8 eee eeee-eeeee [8-eeeeee-8-(eeee-8-ee-8-eeeee)eeeee]eeeeeeeee (88, M8=Me) eee eeeeeeeee ee eeeeeee (8.88eM). Meeee eeeeeee ee 88°M, eeeeee eeeeeeeeee eeee 88 (8.88ee, 8.888eeee, 8eee%) eee eeeee eee eee eeeeeee eee eeeeeee ee 88°M eee 8e. Mee eeeeeee eee eeeeee ee 8°M eee eeeeeeeee ee MeMM (8eM). MeMM8 (8.8eeee, 88.8ee) eee eeeee eee eee eeeeeee eee eeeeeee ee 8°M eee 8e. Mee eeeeeee eee eeeeeee eeee M8M eee eeeeeeeee eeee MeMMe (8×). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8) eee eeeeeeee, eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Meeee eeeeeeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeee/MeMMe 88:8 ee 8:8), eee eeeee eeeeeee eee eeeeeeee ee e eeeee eeeee; eeeee: 88%; ee (eeee/eee) 88:8; 88% ee. Mee ee eee eeeeeeeeee ee 8MMMM (MMMe8) eeeeeeee eeee eee eeeee ee eeeeeeeeeee ee eee eeeeee eeeeeee. Mee ee eee eeeeeeeeee ee eeeeee eeeeeeeeee eeeee MMMM eeeeeeee.

8-{(8M)-8-Meeeee-8,8,8,8-eeeeeeeeeeeeeeee[8,8-e]eeeee-8-ee}-8-eeeeeeeeeeeeee (88, M8=M8=M; M=M; M8=Me); Meeeeee Meeeeeeee:[‌88‌]

8-(Meeeeeeeeeeeee)-8-eeeeee-8M-eeeeee (88, M8=M8=M; M=M; 8.8eeee) eee eeeeee eeeee eeeeee (88, M8=Me; 8.8eeee) eeee eeeeeeeee ee eeeeeee (8eM) eeeee eeeee ee e eee Meeeeee eeee. Mee eeeeeeeee eeee eee eeeeee ee 88°M, eee eeeeee eeeeeeeeee eeee eee-88 (8.88eeee) eee Me eeeeeeee 88 (8.88eeee) eeee eeeee eeeeeeee ee eee eeeeeee. Meee eee eeeeeeee eee eeeeeeee (eeeeeeeee ee MMM ee 8MMMM), eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeee ee eeeee eeeeee eeeeeeeeeeeeee (MeMMe/eeeeeeeee eeeee 8:88 ee 8:8); eeeee: 88.8ee (88%); 88% ee.

(8M)-8-Meeeee-8,8,8,8-eeeeeeeeeeeeeeeeeee (88, M8=Me; M8=M8=M); Meeeeee Meeeeeeee:[‌88‌]

M eeeeeee ee Me(Me)(MMe8) (8eee%), eeeeee eeeeeeeeee eeee 88 (88eee%), Meeeeeee eeeee (8.8 eeeee), eee 8-(8-eeeeeeeeee-8-ee-8-ee)eeeeeee (88, M8=Me; M8=M8=M; 8.8eeee) eee eeeeeee eeee eeeee eee eeeeeeeee ee eeeeeee (8eM) ee e eeeee-eeeeee eeee. Mee eeeeeeeee eeeeeee eee eeeeeee ee 88°M eee 88e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eeeeeeeeeeee ee eee eeeee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeeee eeeee) eeeeeeee eee eeee eeeeeee; eeeee: 88.8ee (88%); 88% ee.

Meeeee (8M,8M,8M)-8-(8-Meeeeeeeeee)-8-eeeeee-8,8,8,8,8,8-eeeeeeeeeeeeeee[8,8,8-ee]eeeeeeee-8-eeeeeeeeeee (88, M8=M8=M; M8=Me; M8=8-MeM8M8); Meeeeee Meeeeeeee:[‌88‌]

Me ee eeee-eeeee eee eeeee-eeeeeee Meeeeee eeee eeeeeee eeee 8-eeeeeeeeeeeeeeeee (88, M8=8-MeM8M8; 8.888eeee), eeeeee eeeeeeeeee eeee 88 (88.8ee, 8.888eeee), eee 8-Å eeeeeeeee eeeeee (888ee) eee eeeeeeeeee 8-(8-eeeeeeeeee-8-ee-8-ee)eeeeeee (88, M8=M8=M; M8=Me; 8.8eeee) ee MM8Me8 (8.8eM) eeeee eeeee. Mee eeeeeee eee eeeeeee eee 88eee eee eeee eeeeee eeee ee 88°M. Me eeeeeeee 88 (8.8ee, 8.88eeee) ee MM8Me8 (8.8eM) eee eeeeeeeeee eee eeeeeee eeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (88; 88.8ee, 8.8eeee) ee MM8Me8 (8.8eM). Mee eeeeeee eee eeee ee 88°M eee 88e, eee eeee eeeeeee ee eeee ee ee 88°M eee eeeeeee eee eeeeeee 88e. Mee eeeeeeeee eeeeeee eee eeeeee ee 8°M eee MeMM (888µM) eee MeMM(MMe)8 (888ee) eeee eeeee. Meeee eeeee eeeeeee ee 8°M eee 88e, eee eeeeeee eee eeeeeee eeee MeMMe (ee 88eM) eee eeeeee eeeeeee e eee ee eeeeee eee. Mee eeeeeeee eee eeeeee eeee eee. MeMMM8 (88eM). Mee eeeeeee eeeee eee eeeeeeeee eeee MeMMe (8×88eM). Mee eeeeeee eeeeee eeee eeeeeeee, eeeeee eeee eeeee, eee eeeee (Me8MM8), eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMMe/eeeeeeeee eeeee 8:88); eeeee: 88.8ee (88%); 88% ee.

(M)-88e-Meeeeee-8,8,88,88e-eeeeeeeeee-8M-eeeeeeeeee[8,8-e]eeeee-8(8M)-eee [88, M8=(MM8)88Me; M8=M8=M]; Meeeeee Meeeeeeee:[‌88‌]

M 8.888M eeee ee MeMe(MMe8) ee eeeeeee (888µM) eee e 8.888M eeee ee MeMMe ee eeeeeee (888µM) eeee eeeeeee eeee eeeeeee (88eM). Meeeeee-8-eeeee eeee [88, M8=(MM8)88Me; 88.8ee, 8.88eeee, 8.8 eeeee] eee eeeee ee eee eeeeeee ee ee eee eee eeeeeeeee eeee eee eeeeeee eee 88eee ee e eeeeee eeeeee. Mee eeee eee eeeeeee eeee eeeeeee (88eM), eee eeeeeeeeee (88, M8=M8=M; 88ee, 8.88eeee, 8 eeeee) eee eeeee ee eee eeeeeee, eeeeeeeeeee eeeeeeee ee eee eeeeeeee ee eeeeee eeeeeeeeee eeee 88 (88ee, 8.88eeee, 8.8 eeeee) ee eee eeeeeee. Mee eeeeeeeeee eee eeee eeeeee ee 88°M eee 88e eee eeeeeeee eee eeeeeee 88e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeee ee MM8Me8 eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, MM8Me8/eeeeeee 88:8) ee eeeeee eeee eeeeeee ee e eeeeeeeee, eeeee eeeee; eeeee: 888ee (88%); 88% ee.

References