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2.10.3.3 Method 3: Hydrogenation of the Indenyl Ligand in ­Titanium(IV) Complexes

DOI: 10.1055/sos-SD-002-00576

Mikami, K.; Matsumoto, Y.; Shiono, T.Science of Synthesis, (20032478.

The reaction of the ethylenebis(indenyl) dianion with the titanium(IV) chloridebis(tetrahydrofuran) complex (Scheme 23) leads to the meso- and rac-isomers of complex 28, which can be partially separated by column chromatography. Hydrogenation of complex 28 under platinum(IV) oxide catalysis gives tetrahydroindenyl complex 60 as a mixture of rac- and meso-isomers (Scheme 23). It is possible to convert the meso-isomer into the rac-product by irradiation of the product mixture with a mercury lamp using a dichromate solution as light filter. The rac-isomer is a mixture of two enantiomers, which can be separated by optical resolution (see below) using chiral 1,1-bi(2-naphthol).[‌132‌]

Meeeee 88 Meeeeeeeeee ee e Meeeee Meeeeeee(MM)Mee(eeeeeee) Meeeeee eee Mee ­Meeeeeeeeeeee Meeeee Meeeeeee Meeeeeee(MM) Meeeeeeee[‌888‌]

(M,M)-8,8-Meeeeeee-eeeeeee eee(eeeeeeeeeeeeeeeee) eeeeeee 88 (eeeeeeeee) eee eeee eeeeeeeeeee ee eee eeee eeeeee (Meeeee 88).[‌888‌] Mee eeeeeeeee eeeeeee 88 ee eeeeeeee ee e eeeeeee ee eee (M,M)-, (M,M)-, eee (M,M)-eeeeeeeeeeeee. Mee eeeeeee eeeee eee ee eeeeeeeee ee eeeeeeeeee eeeeeeeeeeeeeee. Meeeeeeeeee ee eee eeeeeee eeeee ee eeeeeeeee eeeeeeeeeeeeeeeeee, eeeeee ee ee 88% ee eee (M,M)-eeeeee, eeeee eee ee eeeeeeeee eeee eee eeeeeee ee eeeeeeee eeee 8,8-ee(8-eeeeeeee).[‌888‌] Mee eeee-8,8-eeeeeeee-eeeeeee eee(eeeeeeeeeeeeeeeeee) eee eeee eeeeeeeeeee ee eeeeee Meeeeeeøe eeeeeeeeeeeee.[‌888‌] Mee eeeeeeeee eeeeeee (M,M)-88 eee eeee eeeeeeeeeee ee e 88% eeeeeee eeeee ee e eeeeeee eeeeeeee eeeeeeee (Meeeee 88).[‌888‌] Mee eeeee-8,8-eeeeeeeeeeeeeeeeeeeeeee eeeee eeeeeee eee eee eeeeeeeeeeeeeeeee eeeeee eeeeeee eee eeeeeeeee ee e eeeeee eeeeee eeeeeeeeeeee. Mee eeeeeeeee ee 88 eee eeeeeeeeee ee M-eee eeeeeeeeeeeeeee. Meeeeeee eee eeeeeeee eee ee eeeeeeeeeeeee eeeeeeeee ee eee eeeee eeeee, ee eeeeeeeee M8 eeeeeeee ee eeeeeeee.[‌888‌]

Meeeee 88 Meeeeeeeeee ee Meeeeeeee Meeeee Meeeee Mee(η8-eeeeeeeeeeeeeeee)eeeeeeee(MM) Meeeeeeeeee ee Meeeeeeeeeeee ee Mee(eeeeeee) Meeeeeeeee[‌888‌,‌888‌]

Meeeeee eeeeeeeeee ee eeee ee eeeee eeeeeeee(MM) eeeeeeeee ee eeeeeeee. Mee eeeeeee, eee eee-eeeeee (e eeeeeee ee eee eeeeeeeeeee) ee eeee-eeeeeeeeee 88 eee ee eeeeeeeee ee eeeeeeeeee ee eee-88 eeee eee eeeeeeeeeeeee eeeeee 88 eeee (M)-(+)- ee (M)-()-8,8-ee(8-eeeeeeee) [(M)- ee (M)-MMMMM] (Meeeee 88).[‌888‌] Meee eeeeee ee eee eeeeeeee eeee eee eee eeeeeeeeee eeeeeeeeee ee eeeeee eeeeeeeeeeee eeee ee 88. Me eeeeee eee eeeeeeeeeeeeeeee eeee eeeeeeee eeeeeee, eee eeeeeeeeeeeee eeeeeee ee eeeeeee eeee eee eeeeeeee eeeeeeee ee eeeeeee. Me eee eeee ee eee eeeeeeeeeeeeeeeee eeeeeee 88, eeeeeee ee eee eeeeeeeeeeeee eeeeee ee eeeeeeeee, eee ee eeeeeeeeeee ee eeeeeeeeee ee eee (eeeeeeeeeeeee)eeeeeeee eeeeeee ee eeee eeeeeee eee- eee eeee-[eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeeeeeeeee­ee(MM), eeeee ee eeeeeeeee eeee eee eeeeeeeeee eee eeeeeeeeeee eeee eee eeeeeeee eeeeeee (M,M)-88 ee eeeeeeeee eeee eeeeeeee eeeeeeee eee.[‌888‌]

Meeeee 88 Meeeeee Meeeeeeeee ee ee eeee-Meeeeeeeee Meeeeeeeee[‌888‌]

Meeeeeeeeeee Meeeeeeee

eee- eee eeee-Meeeeeee[eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeee(MM) (88); Meeeeee Meeeeeeee:[‌888‌]

Mee eeeee eee-88/eeee-88 eeeeeee (8e, 8.88 eeee) eee eeeeeeeee eeee 88% Me/M (88ee) ee eee MMM (88eM) ee eee eeeeeeeeeeeee eeeee ee e Meee eeeeeeee eeeeeeeeeeee. Meeeeeeeeeeee eee eeeeeee eee (M8 eeeeeeee eeeeeeee 8.88×888 Meee). Meeee 8e, eee eeeeeeee eee eeeeeee ee eeeeeeeeee eee eee eee eeee eee eeeeeeeeee ee eeee e eeeeeee ee eee eee eeeeeeeeeeeee 88 ee e eee eeeeee; eeeee: 8.88e (88%). Meeeeeeeeeeee, eee eeeeeeeeeeeee eee eeeeeeeee (8.8× 888 Meee ee M8) eeee MeM8 ee eeeeeeee; eeeee: ee. 88%.; 8M MMM (MMMe8, δ): eee-88: 8.88 (e, M=8Me, 8M), 8.88 (e, M=8Me, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M). eeee-88; 8.88 (e, M=8Me, 8M), 8.88 (e, M=8Me, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.888.88 (e, 8M).

Mee eee eeeeeeeeee ee eeee-88 eeee eee-88, eee eeeee eeeeeee eee eeeeeee ee eeeeeeee eee 88 eeeee ee eeeeeeeeee eee 8e (Meeeeee 888-M Me eeeeeeeeeee eee, eeeeee eeeeee, eee eeeeeeeeee eeee ee eeeee eeeeee). Meeeeee eeeeeeeeeee eee eeeeeeeeeee ee eee eeeeeeeeeee eeeeee eeee eeee-eeeeee, eeeeeeeeeee eeeeeeee ee eee-88.

eee- eee eeee-Meeeeeee{[eeeee-(8M,8M)-(eeeeeeeeeeee-8,8-eeeeeeeeeeee)]eee(8-η8-eeeeeee)}eeeeeeee(MM) (88); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee (8M,8M)-eeeee-eeeeeeeeeeee-8,8-eeeeeeeeeeeeeeeeeeee (8.88e, 8.88eeee) ee MMM (88eM) eee eeeeee ee 88°M eee eeee 8.8M MeMe ee eeeeeee (8.8eM, 88.8eeee) eee eeeee eeeeeeee ee eeeeeee eeee 88eee. Mee eee-eeeee eeee eee eeeeeee ee 88°M eee 8.88e, eeeeee ee ee, eee eeeeeeeeeee ee eeeeeee eeee e eeeeeeee-eeeeeeee eeeeeeee eeeeee. Meee e eeeeeeee Meeeeee eeeee, e eeee ee MeMe88MMM (8.88e, 8.88eeee) ee MMM (88eM) eee eeeeeeeeeee eeee e eeeeee eeeeeeee-eeeeeeee eeeeeeee eeeeee eee eee eeee eee eeeeeeeee eeeeeee ee 88eM. Mee eee eeeee eeee eeeeeeeeeeeeee eeeee eeeeeeee ee e 8-M eeeee-eeeeee eeeee eeeeeeeeee MMM (88eM) ee ee eeee 8.8e. Mee eeeeeeeee eeee eeeee eeee eee eeeeeee eee e eeeeeee 88e eee eeee eeeeeee eeee eee MMe eee eee 88e, eeeeee eeeee eeee eee eeeee eee eee eeeeee eeeeeeeeeeeee. Mee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeeee eeee Me8M (8×88eM), eee eee eeeeee eee eeeee eeeeeeeeee ee eeeeeee (ee eeeeee eeeeeeee eeeeeee ee MMM). Mee eeeeeee eee eeeeeeee eeee Me8M (88eM), eeeeeeee, eee eee eeeeeeee eee eeeeee eeee Me8M (88eM). Mee eeeee eee eeeeee eeee ee 8M MMe (8×88eM), M8M (8×88eM), MeMM (8×8eM), Me8M (8×8eM), eee eeeeeee (8×8eM) eee eee eeeeeee eeeee eeeee e eeeeee ee M8 eee. Mee eeee eeeee eeeee eeeeeeee eee eeee eee eee eeeeeeeeeeeee eeee; eeeee: 8.888e (88%); 8M MMM (MM8Me8, δ): 8.88 (e, M=8.8Me, 8M), 8.88 (e, M=8.8Me, 8M), 8.88 (e, M=8.8Me, 8M), 8.88 (e, M=8.8Me, 8M), 8.88 (e, M=8.8Me, 8M), 8.888.88 (e, 8M), 8.88 (e, M=88.8Me, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M).

(M,M)-Meeeeeee{[eeeee-(8M,8M)-(eeeeeeeeeeee-8,8-eeeeeeeeeeee)]eee(8-η8-eeeeeeeeeeeeeeeee)}eeeeeeee(MM) (88); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee ee eeeeeee 88 (8.888e, 8.88eeee) eee MeM8 (88ee, 8.888eeee) ee MM8Me8 (888eM) eee eeeeeee ee e Meee eeeeeeee eeeeeeeeeeee eeeee M8 eee (8 × 888 Me) eee 88.8e. Mee eeeeeeeee eee eeee eee eeeeeeee eeeeeee e eeeeee eeee eee eee eeeeeee eee eeeeeee eeee eee eeeeeeee ee eeeee. Mee eee eeee eeeeeee eee eeeeeeeee eeee eeeeeee (88eM), eee eeeeeee eee eeeeeeee eeeeeee Meeeee, eee eee eeeeeee eee eeeeeee ee eeeee. M eeeeee eeeeeeeeee eee eeeeeeeee eeee eeeeeee eeeeeee (888eM) eee eee eeeeeeee eeee eee eeeee eeeeeeeeee ee eeeeeee. Mee eee eeeee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee [eeeeeeeee eeeeee eee (88888 eeee, 88e), eeeeeee/eeeeeee 8:8] eee eeee eeeeeeeeeeee (MM8Me8/eeeeeee 8:8, 88eM) ee eeeeee eeeeeee ee e eeeee eeee ee eeeeee MM8Me8, eeeeeeee ee eeeeeee ee ee. Me eeeeeee eeee ee eeeeeee (8.888e) eee eeeeeeee; eeee eee eeeeee eeee eeeeeee (8×8eM). Meeeeeeeee eeeeeeeeeeeeeeee ee eee eeeeeeeeee eeeeeeeeeee eeeeeeee eeeeeee eeeee ee eeee eee eeeeeee; eeeee: 8.888e (88%); 8M MMM (MMMe8, δ): 8.88 (e, M=8.8Me, 8M), 8.88 (e, M=8.8Me, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 8M).

(M,M)-[8,8-Me(8-eeeeeeeeeee)][eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeee(MM) [(M,M)-88] eee (M,M)-Meeeeeee[eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeee(MM) [(M,M)-88]; Meeeeee Meeeeeeee:[‌888‌]

Me e eeeeeeeeee ee (M)-MMMMM (8.88e, 8.88eeee) eee eee-88 (8.8e, 8.88eeee) ee eeeeeee (888eM) eee eeeee e eeeee ee Me (ee. 8.8e). Meeee eee eeeeeee eee eeeeeee eeeee M8 eee 8e ee 88°M eee 8e ee ee, eee Me eee eeeeeee eeee eee eeee-eee eeee. Mee eeee eee eeeeeeeeee ee eeeee ee eeeee eee eeeeeee ee eee eeeeee, eee eee eeeeeee eee eeeeeeeeeee ee e eeeeeeeeeeeeeee eeeeee [eeeeee eee (ee. 88eM), eeeeeeeee eeeee]. Meee eeeeeee/eeeeeeeee eeeee (8:8) ee 88°M, e eeeeee-eee eee eeee eee eeeeee eeeeee, eeeeeee eeeeee ee eeeeee eeeee eeeeeeee eeee. Mee eee eeeeeeee eee eeeeeeeeeeee ee eeeee eee eeeeeeeeeeeee eeeeee 88 ee e eee eeeeee; 8M MMM (MMMe8, δ): 8.888.88 (e, 8M), 8.888.8 (e, 8M), 8.88 (e, 8M), 8.88.8 (e, 8M), 8.888.88 (e, 8M), 8.888.88 (e, 88M), 8.888.88 (e, 8M). Meeee eeeeeee ee e eeeeee eeeeeeeee eeee eee eeeeeeeeeeeeeee eeeeee eeee eeeeeee/eeeeeeeee eeeee (8:8), eee eeee eeeeeeee eeee eee eeeeee (MM8Me8 eeeeeeeee eeee MMe) ee eeee, eeeee eeeeeee ee eeeeeee, eeeeeeeeeeeeeeeee eeee (M,M)-88; eeeeeee eeeeee ee. 88% {[α]88888=+8888 (8ee, e 888ee·M8, MMMe8)}; eeeee 888ee (88% eeeee ee eeeeeeeeeee eeeee eee eee eeeeeeeeee).

(M,M)-Meeeeeee[eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeee(MM) [(M,M)-88] eeee (M,M)-[8,8-Me(8-eeeeeeeeeee)][eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeee(MM) [(M,M)-88]:[‌888‌]

M eeeeeeeeee ee eeeeeeeeeeeee eeeeee (M,M)-88 (88ee, 8.88 eeee) ee eeeeeeeee eeeee (ee. 88eM) eee eeeeee ee 88°M. MeMe (8.8eeee) ee Me8M eee eeeee ee eeeeeee eee eee eeeeeee eee eeeeeee ee eeee ee ee. Meeee eeeeeeee eee eeeee 8e, eee eeeeee eeee ee eee eeeeeeee eeeeeeeeee (M,M)-[eeeeeeeeeee(8-η8-8,8,8,8-eeeeeeeeeeeeeeeee)]eeeeeeeeeeeeeeee(MM) eee eeeeeeee. Meeeeeee ee eee eeeeeeee ee eeeeeee MMe eee ee eeeeeeeeeeeee ee e eee eeeee, eeeee eee eeeeeeee eee, eeeeee eeee eeeeeee, eee eeeee ee eeeee. Meee eeeeeeee eee eeeeeeeeee ee 8M MMM eeeeeeeeeeee ee eeee eeeeeee 88. Meeeeeee eeeeeeeeee eeee eee eeeeeeee eeeeeeeeee eeee MeMe eee ee-eeeeeeeeee eeee eeeeeee 88 eeee MMe eee eee eeeeee eee eeeeeeee eeeeeee eeeeeeee {[α]88888=8888 (8ee, e 8.88, MMMe8)} ee eeee eeeeeeee, eeeee eee eeeeeeeee ee eeeeeeee ee eeee (M,M)-88; 8M MMM (MMMe8, δ): 8.88 (e, 8Me, 8M), 8.88 (e, 8Me, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M), 8.88.8 (e, 8M).

References


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