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47.1.1.5.3.1 Variation 1: Cyclization of Aliphatic Dialdehydes, Diketones, and Oxoaldehydes

DOI: 10.1055/sos-SD-047-00141

Takeda, T.; Tsubouchi, A.Science of Synthesis, (201047288.

Alicyclic alkenes of all ring sizes from three to 22 are readily prepared by the intramolecular McMurry coupling of alkane-α,ω-diones (Scheme 34).[‌1‌,‌82‌,‌144‌,‌145‌] Strained cyclopropenes 110 are prepared by intramolecular coupling of 2,2-dimethylpropane-1,3-dione 109 (R1=Me) and the diethyl analogue 109 (R1=Et) using titanium(III) chloride/lithium aluminum hydride.[‌145‌] Attempts to prepare the cyclopropene ring by the coupling of easily enolizable 1,3-diphenylpropane-1,3-dione (109, R1=H) and the 2-monomethyl derivative are unsuccessful. A similar intramolecular cyclization of diones 111 successfully proceeds to produce the 1,2-diphenylcycloalkenes 112 with larger rings (ring sizes 46, 810, and 12).[‌144‌] The cycloalkenes 114 of all ring sizes from 4 to 16 and even 22 have also been obtained in good yields by the intramolecular reductive coupling of dicarbonyls 113 with titanium(III) chloride/zinccopper couple.[‌1‌] The benzo-fused cycloheptene 116 has been prepared similarly from the oxoaldehyde 115.[‌1‌] Improved results are obtained in the formation of the 14-membered cycloalkenes 118 from dicarbonyl compounds 117 using titanium(III) chloridedimethoxyethane solvate/zinccopper couple.[‌82‌] Dithienylperfluorocyclopentene 120 is prepared by ring closure of the 1,5-diketone 119 with titanium(III) chloride tetrahydrofuran solvate/zinc.[‌145‌]

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Meeeeeeeeee 88

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

Mee eeeeeeeeeeeeee MeMeeee eeeeeeee ee eeeeeeeeee eeeeeeeee eee eeee eeeeeeee eee eee eeeeeeeeeee ee eeeeee eeeeee (Meeeee 88).[‌888‌‌888‌] Meeeeeeeeeeeee eeeeeeee ee eee eeeeeeeeeee eeeeeeeeeee 888 eeeee eee eeeeeeeee-8,8-eeee-8-eeee 888 eeee eeee eeeee eeee 88 ee 88.[‌888‌] Meeeeeee ee eee eeeeeeeeeee 888 (e=8, 8) eeeeeeee eeee ee eeee eeeeeeeeeee, eeeeee eeee eeeeeeee eeeeeeeeee (eeeeeee 8,8-eeeeeeeeeeeeeee) eee eeeeeeee eee eee eeeeeeeeeee ee eeeeee eeeeeeeeee 888 (e=88). Mee eeeeeeee (8-eeee/88-eeee, eee 8-eeee/88-eeee) eeeeeeeeeee 888[‌888‌] eee eeeeeeee (8-eeee/88-eeee) eeeeeeeeeee 888[‌888‌] eee eeeeeeee ee eee eeeeeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeee 888 eee 888, eeeeeeeeeeee.

Meeeee 88 Meeeeeeeeee ee Meeeee Meeeee ee Meeeeeeeeeeeee MeMeeee Meeeeeee ee Meeeeeeeee Meeeeeeee[‌888‌‌888‌]

Meeeeeee eeeeeeeee eeee e eeeeeeeeee eeeeee eeee eeee eeee eeee eeeeeeee ee eeeeeeeeeeeeee MeMeeee eeeeeeee ee eeeeeeeeee eeeeeeeee (Meeeee 88).[‌888‌,‌888‌] Meee, eee eeeee-eeeee (M)-(+)-[88.88]eeeeeeeeeeee (888, e=8) eee (M)-(+)-[88.88]eeeeeeeeeeee (888; e=8) eee eeeeeeee eeee eee eeeeeeeeeee (+)-888 (e=8, 8) ee eeeeeeeee eeee eeeeeeee(MMM) eeeeeeee/eeeeeee.[‌888‌] Mee eeeeeeeeeeeee eeeeeeee ee eeeeee eeeeeee 888 eeeeeeee ee eee eeeeee eeeee ee eeee ee eeee eeeeeeeee eeeee eeeee eee eeeeeeeeeeeeee 888 eeeeee e eeeeeeeeee eeeeee eeee.[‌888‌]

Meeeee 88 Meeeeeeeeee ee Meeeeeee Meeeeee eeee e Meeeeeeeee Meeeee Meee ee Meeeeeeeeeeeee MeMeeee Meeeeeee ee Meeeeeeeee Meeeeeeee[‌888‌,‌888‌]

Meeeeee eee eeeeeeeeeeeeee MeMeeee eeeeeeee ee ee eeeeeeeee eeeeee eee eee eeeeeeeeeeee ee eeeeeeeeeee ee eeeeeee eeee eeeee eee eee ee eeeeeee eee eeeeeeeeeeee ee eee eeeeeeee ee e eeeeeee ee eeeeeeeeee eeeeee ee eeeeee eeeeee ee eee eeeeeeee eee eeeeeeee eeeeeeeeee, eeee eeeeeeeeeeee ee eee eeeee eeeeeeeee ee eeeeeee eeeeeeee eeee eeeeeeee ee eee eeeeeeeeee. Mee eeeeeee, ee eeeeeeeeeeeeeeee eeeeeeeee ee eeeeeeeeee eeeeeeee (+)-eeeeeeeeee (888) eee eeee eeeeeeee eeeee eee eeeeeeeeeeeeee MeMeeee eeeeeeee ee eeeeeeee 888 ee eeee eee eeeee eeee eeeeee 888 ee e eee eeee (Meeeee 88).[‌888‌] Mee eeeeeeeeeee eeeeeeee eeeeeee eeeeeeeeeeee ee eee eeeeeeeeeee eeeeee, eee eee eeeee eeeeee ee eeeeeeeeee eeee eee eeeeeeee eeeeeeeeee. Me eeeeeeee 88-eeeeeeee eeeeeeeeeee eeeeeeeeee eeeee 888 eee eeee eeeeeeeeeee ee e eeeeee eeeeeeeeeeee eeeeeeeee eee eeeeeeeeeeeeee eeeeeeee eeeeeeee ee eee eeeeeeeeee 888.[‌888‌] Mee 88-eeeeeeee eeee ee eee eeeeeee eee eee eeeeeeee ee eee MeMeeee eeeeeeee.

Meeeee 88 Meeeeeeee ee (+)-Meeeeeeeee eee ee Meeeeeee 88-Meeeeeee Meeeeeeeeee Meeeeeeeee Meeee Meeeeeeee eee Meeeeeeeeeeeee MeMeeee Meeeeeeee[‌888‌,‌888‌]

Meeeeeee eeeeeeee ee eee eeeeeeeeeee ee MeMeeee eeeeeeeee ee eeeeeee eeeeeee eeeeeeeee eee eeeeeeeeee ee Meeee 8.[‌888‌‌888‌] M eeee eeeeeee ee eeeee eeee eeeeeeeee eeeee eee eeeeee ee eee eeeeeeee. Meee-eeeeeeee eeeee eee eeeeee ee eee eeeeeeeee ee (±)-eeeeeee[‌888‌] (eeeee 8) eee (±)-eeeeeeeee.[‌888‌] Meeeeeee eee-eeeeeeee eeee eeeeeeeeee eeee eeee eeeeeeee ee eee eeeeeeeee ee (+)-eeeeeeeee[‌888‌] (eeeee 8) eee (±)-eeeeeeee,[‌888‌] eee eeeeeeeee eee-eeeeeeee eeeeeeeee ee (±)-eeeeeeeeeeee (eeeee 8).[‌888‌] Meeeeeeeeee eeeeeeeee eeeeeee-8 (eeeee 8) eee eeee eeeeeeeeeee ee eeeeeeeeeee ee e eeeeeeeeee ee e eeeee-eeeeeeee eeee ee eee eeeee eeeee.[‌888‌] M eeeeeeeee eeeeee eeee ee eeeee-eeeeeeee eeee eee eeee eeeeee ee eee eeeeeeeee ee eeeeee (eeeee 8).[‌888‌] Mee-eeeeeeee eeee eeeeeeeeeeeeee, eeeeeeeeeeeeeeeee[‌888‌] (eeeee 8), eeeeeeeeee,[‌888‌] eee eeeee eeeeeeeeeeeee, eee eeeeeeeeeeeeeeeeeee[‌888‌] eeee eeee eeeeeeee ee eeeeeeeee eeeeee eeee eeeeeee eee eee-eeeeee eeeeeeee-eeeeeeee eeeeeeeeeee. Meeeee-eeee eeeeeeeee ee eeeeeeeeeeeee eeeeeeee ee eeeeeeee ee eee eeeeeeeee ee eeeeeeeee eeeeeeeeeeee eeeeeeee[‌888‌] (eeeee 8) eee eeeeeeee.[‌888‌] Meeeee-eeee eeeeeeeee ee eeee ee eee eeeee eeeeeeeee ee eeeeeeeeeeee[‌888‌] (eeeee 8). Mee eeeeeeeeeeeeee MeMeeee eeeeeeee eee 88-eeeeeeee eeee eeeeeeeee eee eeeee eeee eeeeeeee ee eee eeeeeeeee ee eeee eeeeeeeeeee eeeeeeeeee eeee ee eeeeeeee-M[‌888‌] (eeeee 8), (+)-8,8-eeeeeeeeeeeee-M,[‌888‌] (+)-88,88-eeeeeeeeeeeee-M,[‌888‌] ()-88-eeeeeeeeeeeeeeeeee,[‌888‌] ()-88-eeeeeee-88,88-eeeeeeeeeeeeeeee[‌888‌] (eeeee 88), (±)-eeeeeeeeeeee M eee M[‌888‌] (eeeee 88), (±)-eeeeeeeeeee M eeeeee eeeee,[‌888‌] eee (±)-eeeeeee eeeeeee eeeeee eeeee.[‌888‌] Meeeeeeee ee eee eeeeeeeee eeeeeeeeeee,[‌888‌] eee eeeeeeeeeeeee eeeeeeeeeee[‌888‌] (eeeee 88) eeeeeee eee eeeeeeeee ee 88-eeeeeeee eeeee.

Meeee 8 Meeee Meeeeeeee ee Meeeeee Meeeeeee ee Meeee ee Meeeeeeeeeeeee MeMeeee Meeeeeee[‌888‌‌888‌]

Meeee Meeeeeeee Meeeeee Meeeeee Meeeee (%) Meeeeee Meeeeee Meeeee Mee
8 MeMe8, Me/Me 88 [‌888‌]
8 MeMe8, M8M 88 [‌888‌]
8 MeMe8, Me/Me 88 [‌888‌]
8 MeMe88.8(MMM), Me/Me 88 [‌888‌]
8 MeMe8, Me/Me 88 [‌888‌]
8 MeMe8, Me/Me 88e [‌888‌]
8 MeMe88.8(MMM), Me/Me 88 [‌888‌]
8 MeMe8, Me/Me 88e [‌888‌]
8 MeMe8, Me 88 [‌888‌]
88 8. MeMe8, Me, eeeeeeee
8. MMMM, MMM
88e [‌888‌]
88 MeMe8, Me, eeeeeeee 88 [‌888‌]
88 MeMe8, Me/Me 88 [‌888‌]

e Meeee ee eee MeMeeee eeeeeeee.

e Meeeeeeee eee M-eeeeee; eee eeeee (M/M) 88:88.

e Meeeeee ee eeeee eeeeeeeeee eee M/M eeeeee eeee eeeeeee (eeeee ee. 8:8:8). Meeee eeeeee eeeee.

e Meeee ee eeee eeeeeee. Meeee ee eeeeeeeeeeee eeeee MMMM ee 88%.

Meeeeeeeeeee Meeeeeeee

(M)-(+)-[88.88]Meeeeeeeeeee [(M)-(+)-888, e=8]:[‌888‌]

M eeeeeee eeeeee ee MeMe8 (8e, 88.8eeee) eee Me (8.88e, 88.8eeee) ee MMM (88eM) eee eeeeee eeeee eeeeee eeeee eeeee eee 8e. M eeee ee eeeeeeeeee (+)-888 (e=8; 888ee, 8.88eeee) ee MMM (88eM) eee eeeee eeee 88e eeee e eeeeeee ee eee eeeeeeeee eee-eeeee eeee eeee eeeee eeee. Mee eeeeeee eee eeeeee eeeee eeeeee eee 8e. Meeeee (88e) eee eeeee ee eee eeeeee eeee, eee eee eeeeeeeee eeeeee eee eeeeeeee eeeeeee e eee ee Meeeee eee eeeeee eeee eeeeee. Meeee eeeeeee ee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eeeeeee eee eeeeeee ee e eeeeee eee eeeeee eeeeee eeee e eee ee Meeeeeee eee eeeeee (eeeeee). Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeeeee eee eeeeeeee ee eeeeeeeeeeeeee (eeeeee eee, eeeeee) ee eeee eee eeeee eeeeeeee; eeeee: 888ee (88%).

References


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