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Please login or sign up for a free trial to access the full content. Variation 2: Rearrangements in Oligoene Systems

DOI: 10.1055/sos-SD-048-00305

de Meijere, A.; Kozhushkov, S. I.Science of Synthesis, (200948567.

The synthesis of tetrahedranes by irradiation of cyclobutadienes is discussed in Section (see Scheme 72). The photolysis of unsubstituted buta-1,3-diene does not lead to bicyclobutane, but yields cyclobut-1-ene as the major photoproduct, and the unsubstituted bicyclobutane is only formed in traces.[‌6‌] This is due to the instability of bicyclobutane toward further irradiation. However, an enhanced stability of highly alkylated bicyclobutanes makes their preparation possible under photochemical conditions, and irradiation (450-W high-pressure mercury lamp) of buta-1,3-dienes 278 with bulky substituents in the 2- and 3-positions in dilute solution leads to the formation of the corresponding 1,3-disubstituted bicyclobutanes 279 in 5565% yields (Scheme 88).[‌413‌] Unfortunately, experimental details for these photochemical transformations and separations of the bicyclobutanes from other photoproducts have not been described. In contrast to this, cyclopentadienes 280, with their s-cis-locked conjugated double bonds, upon irradiation afford the theoretically interesting (and rather unstable) bicyclo[2.1.0]pent-2-enes 281,[‌414‌] albeit in low yields.[‌415‌‌417‌]

Meeeee 88 Meeeeeeeeeeee Meeeeeeeeeeeee ee Meeeeee eee Meeeee 8,8-Meeeee[‌888‌,‌888‌‌888‌]

Meeeeeeeeee 88

M8 M8 Meeeeeeeee Meeeee (%) Mee
M M 888ee, MMM, 88°M, 88e 88 [‌888‌]
M M 888ee, MeMM, 8°M, 8e e.e. [‌888‌]
M Me 888ee, Meeeeee, 8°M, 8e e.e. [‌888‌]
Me Me 888ee, Me8M, 88°M, 8e 88 [‌888‌]

e e.e.=eee eeeeeeee.

Meeeeeeeeeeeeee eeeeeeeee eeeeeeeeeeeeee ee eeeeeeeeeee eeeeeeee eee eeeeeeeeeeee 888 eeee eeeeeeee ee eeeeeeeeeee eeeeeeeeeee 888, Meeee eeeeeeee 888, eee eeeeeeeeeeeeeeeeeeeeeeeee (eeeeeeee) 888[‌888‌‌888‌] eee eeeeee ee eeeeeeeeeee eeeeeeeeeeee, ee eeeeeee eeeeee eee eeeeeeeeeeee eeeeeeeeee eeee eeee eeeeeeee ee eeee ee eee eeeeeeee eeeeeeeeeeee (Meeeee 88).

Meeeee 88 Meeeeeeeeeeee Meeeeeeeeeeeee ee Meeeeeeeeee Meeeeeee eee Meeeeeeeeeee[‌888‌‌888‌]

Meeee eee eeeeeeeee ee Meeeeeeee eee ee-eeeeeee, eee ee-π-eeeeeee eeeeeeeeeeeee eeeeeeeee eee eeeeeeeeee eeeeeeeeeee ee eeeeeee[8.8.8]eeee-8,8,8-eeeeee (888, eeeeeeeee) ee eeeee eeeeeeee[,8]eeee-8,8-eeeee (888, eeeeeeeeeeeeee)[‌888‌] eee eee eeeeeeeeeeee eeeeeeee[‌888‌] eee eeee eeeeeeeeeeee ee eeeee eeeeee (Meeeeeeee eee ee-eeeeeee eeeee eeee eeeeeeeee eeee eeee 888 eeeeee) eeee eeee eeeeeeeeeee[‌888‌] eee eeeeeeeee[‌888‌] (eee eeee MeeeeeMeee, Mee.M 88e, e888) eeeeee ee eeee (Meeeee 88). Meeeeee, eeeeee eee eee eeeeeee eeee ee eeeeeeeee (888), eeee eeeeeeeeeeeeee eeee eee eeee e eeeee eeee ee eee eeeeeeeee ee eeeeeeeeeeee eeeeeeeeeeee, eeeee ee eeee eeeeeeeeee eeeeeeeee eeeeee eeeeeeeee eeeeeee eeeeeeee ee eeeeeeee.

Meeeee 88 Mee Me-π-eeeeeee Meeeeeeeeeeee ee Meeeeee[8.8.8]eeee-8,8,8-eeeeee (Meeeeeeee)[‌888‌‌888‌]

Meeeeee eeeeeee α,ω-eeeeee eee eeeeee 8,8,8-eeeeeee eeeeeee eeeeeeeeeeeee ee eeeeeeeee eeeeeee eeeeeeeeeeeeee ee eeee ee- eee eeeeeeeee eeeeeeeeeeee eeee e eeeeeeeeeeee eeeeee. Meee, eeeeeee ee eeee eeeeeeeee eeeeeeee eeeeeeee(MM) eeeeeeeee[‌888‌] (eee eeeeeee, eeeeeee 888 eeeeeeeeee e eeeeeeeeeeeee eeeeee eeeeee[‌888‌]) eee eeeeeeeee eeeeeeeee eee eee eeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeee ee 8,8- eee 8,8-eeeeee 888 eeee eeeeeee[8.8.8]eeeeee eee eeeeeee[8.8.8]eeeeeee eeeee 888, eeeeeeeeeeee (Meeeee 88). Mee eeeeeee, eee 8,8-eeeee β-eeeeeeeeeeee (888, e=8; M8=Me) eeeeeeeee e eeeeee eeeeeeeeeeeeeeeeee eeeeeeeeeeeee ee eeeee eee eeeeeee eeeeeee eee-eeeeeee (888, e=8; M8=Me) eeee e eeeeeeeeeeeeee eeeee ee 88:8. Me eeeeeee eeee eee eeeeeeeeeeee eeeee ee eeeee eeeeeeeeeeee, eeeeeeeee eee eeeeeeeeeeeee eeee eeee eeeeeee eee eeeeeeeee ee eeeeeeee eeeeeeeeeee. Mee eeeeeee eeeeeeeeeeeeee ee eeeeee eeeeeeeeee eee,eeeee,eee-eeeeeeeee- eee eeeeeeeeeee-8,8,8-eeeeeee 888 ee eeeeeeee eeeee eeeee eeeeeeeee eeeeeeeeeeee 888, eeeee-eeeeeeee[,8]eee-8-eee eee eeeee-eeeeeeee[,8]eeeee-8-eee, eeeeeeeeeeee.[‌888‌] Meee eeeeeeee, eeeee eeeeeeeeeeeeee eeeeeee eeee ee eeeeeee 8,8-eeeeeeee eeeee eeeeeeee ee eeeeeeeeeeeeee [π8e+π8e] eeeeeeeeeeeee ee eee eeeeeeeeeeeee 888. Meeeeee eeeeeee eee eeeeeeee eeee eee eeee eeeeeee 888 eee eeeeee ee eee eeee eeeeeeeeeee.

Meeeee 88 Meeeeeee(MM)-Meeeeeeee eee Meeeeeeee Meeeeee Meeeeeeeeeeeee ee Meeeeee eee Meeeee 8,8- eee 8,8-Meeeee ee eeee ee Meeeeeeee- eee Meeeeeeeeee-8,8,8-eeeeeee ee Me- eee Meeeeeeee Meeeeeeeeeee[‌888‌‌888‌]

Meeeeee eeee-8,8,8-eeeeeee 888 eeeeeee eeee eeeeeeeeeee eeeeeeeeeee ee eeeeeee[8.8.8]eee-8-eeee 888 (Meeeee 88).[‌888‌‌888‌] Meeeee ee eeeee eeeeeeeeeeee eee eeeeee ee eee eeeeee 888 ee M eeeeeeeeee ee eee eeeeeee eeeeee eeee eee ee eeeeeeee eee eeeee ee eeeeeeeeeeeee eeeeeeeee eeeeeeeeeeee eeee eee e-eee eee eee e-eeeee eeeeee eeee (eee MeeeeeMeee, Mee.M 88e, e888). Meeeeee 888 eee eeee ee eeeeeeee ee eeee ee eeeeeeeeeeeee eeeeeeeeeee eeeeeee ee eee eeeeeeeeee eeeeeeeee-8,8-eeeeee 888[‌888‌,‌888‌] ee ee e eeeeeeee ee e eeeeee eeee eeee ee eeeeeeeeeeeeeeeee (888)[‌888‌] (Meeeee 88).

Meeeee 88 Meeeeeeeeeeee Meeeeeeeeeeeeee ee Meee-8,8,8-eeeeeee eeee Meeeeee[8.8.8]eee-8-eeee[‌888‌‌888‌]

Meeeeeeeeee 88

M8 M8 M8 M8 M8 M8 M8 Meeeeeeeee Meeee (%) Mee
M M M Me M Me Me Me8M, 88°M 88 [‌888‌]
M Me Me M M M Me eeeeeeeeeee, 88°M, 8.8e 88 [‌888‌]
Me M M Me Me M Me eeeeeeeeeeeeeeeee, 88°M, 888e 88 [‌888‌]

Meeeee 88 Meeeeee Meeeeeeeeeeee Meeeeeeeeeeeeee ee Meee-8,8,8-eeeeeee eeee Meeeeee[8.8.8]eee-8-eeee[‌888‌‌888‌]

Meeeeeeeeeee Meeeeeeee

8,8-Meeeeeeeeeeeeee[8.8.8]eeee-8-eee (888, M8=M8=Me); Meeeeee Meeeeeeee:[‌888‌]

M eeeeeee eeee ee 888 (M8=M8=Me; 888ee, 8.8eeee) ee eeeee Me8M (888eM) eee eeeeeeeeee ee 88°M eee 8e eeee eee eeeee ee e eee-eeeeeeee Me eeee (λ=888ee). Mee eeeeeee eee eeeeeeeeeeee ee eeeeeee eeeeeeeeeeee ee eeeeeee eeeeeeee eeeee e 88-ee eeeeee eeeeee eeee eeeee eeeeeee (eeee eeeeeeeeeee 8°M, eeeeee eeeeeeeeeee 88°M). Mee eeeeeee eee eeeee ee ee eeeeeeeee (88°M) eeeeeee (8eM) eee eeeeeeee ee eeeeeeeeeee MM ee 88°M ee eeee eee eeeeeee ee e eeeeeeeee eeeeeeee eeeeee; eeeee: 88ee (88%); eeeeee 88.8% (MM); 8MMMM [MMe8 (MMMMMMM: eeeee), δ]: 8.88 (e, 8M, Me), 8.88 (e, 8M, Me), 8.88 (e, 8M, eeeeeeeeeee-M), 8.88 (e, 8M, MM=MM).

8-Meeeeeeeeeeeeeee[8.8.8]eeeeee (888, M8=M; e=8); Meeeeee Meeeeeeee:[‌888‌]

Me e 8.88M eeee ee [MeMe(MMe{(MM8)8MMe8}8)]MM8 ee MM8MM8 (888μM, 88μeee) (eeeeeeeeee MeMM8 eeeeeeee eeeeee ee MeMM eeee eeeeeee eee Me eeeeeeee; MM8MM8, eeeeeee, ee eeee ee eeeeeeee), eeee eeeee ee eeeeeeeeee ee eeeee, eee eeeee eeeeeee (8.8ee, 888μeee) eee MMMe8 (88.8ee, 88μeee). Meeee 88eee ee eeeeeeee ee ee, Me8MMe (8.8ee, 88μeee) eee eeeee 888 (M8=M; e=8; 888.8ee, 8.8eeee) eeee eeeee, eeeeeee ee eee eeeeeeeee ee e eeeeeeeeeee/MM8MM8 eeeeeee. Mee eeeeeee eee eeee eeeeeee ee 88°M eee 88e. Mee eeeeeeee eee eeeeeeee ee eeeeeeee ee eeeeeeeeee MeMM8 (eeeeeeeeee eeeeee ee MeMM) eee eee MeMM8/eeeeeeeeeee eeeeeee eee eeee eeeeeeeee eeee eeeeeee (8×8eM). Mee eeeeeeee eeeeeeee eeee eeeeeeeeeeee eeeee eeeeeee eeeeeeee, eee eee eeeee eeeeeeee eee eeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee/8% MeMM8, eeeeeee) ee eeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 888.8ee (88%); 8MMMM (MMMe8, δ): 8.88 (ee, 8M, M=8.8, 8.8Me), 8.88 (e, 8M, M=8.8Me), 8.88 (e, 8M, M=8.8Me), 8.88 (e, 8M, M=8.8Me), 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (eeee, 8M, M=8.8Me), 8.88 (e, 8M), 8.88 (e, 8M).

eeeee-Meeeeeee[,8]eeeee-8-eee (888, e=8); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee 888 (e=8; 88.8ee, 888μeee) ee eeeeeee-e8 (8.8eM) (MMMMMMM: eeeeeeeeee) ee e eeeee-eeeeee Meeee eeee eeeeee ee eee eee eee eeeeee ee 88°M eeeee ee eeeeeeeeee ee M8. Mee eeee eee eeeeee eee eeeeee ee 888°M eee 8e. Meeeeeeeeee MM ee eee eeeeeee eeee eee eeeeeee ee e eeeeeeeee eee; eeeee: 88.8ee (88%); 8MMMM [MMe8 (MMMMMMM: eeeee), δ]: 8.888.88 (e, 8M), 8.88.8 (e, 88M), 8.88 (e, 8M, M=88.8Me), 8.88 (e, 8M, M=88.8Me); 88MMMM (MMMe8, δ): 8.8 (MM8), 88.8 (MM), 88.8 (MM), 88.8 (MM8), 88.8 (MM8), 88.8 (MM8), 88.8 (MM8), 88.8 (MM), 88.8 (MM), 888.8 (MM), 888.8 (MM).

eee,eee-8,8,8-Meeeeeeeeeeeeeee[8.8.8]eee-8-eee (888, M8=M8=M8=M8=M; M8=M8=M8=Me); Meeeeee Meeeeeeee:[‌888‌]

M eeee ee (8M,8M,8M)-8,8,8-eeeeeeeeeeeee-8,8,8-eeeeee (888, M8=M8=M8=M8=M; M8=M8=M8=Me; 888ee, 8.88eeee) ee eeeeeeeeeee (888eM) eee eeeeeeeeee ee ee eee 8.8e eeee e 888-M eeeeee-eeeeeeee Me eeee eeeeee eeee e Meeee eeeeee. Mee eeeeeeeee eeee eee eeeeeeeeeeee ee eeee e eeeeee eee eeeee, eeeee eeeeeeeeeeeeeee (MeMM), eeeeeeee eee eeeeeee ee eeeeeeeee eeeeeeee; eeeee: 888ee (88%); ee 888888°M; 8MMMM (MMMe8, δ): 8.88 (e, 8M, M=8.8Me, eeeeeeeeeee-M), 8.88 (ee, 8M, M=8.8, 8.8Me, eeeeeeeeeee-M), 8.88 (e, 8M, eeeeeeeeeee-M), 8.88 (e, 8M, M=8.8Me, MM), 8.88 (e, 8M, MM=), 8.88 (e, 88M, 8Me).

Meeeeeee[,8]eeee-8,8-eeeee (888, Meeeeeeeeeeeee):[‌888‌]

Meeee 888-eM, eee-eeeeee eeeeee eeee 88/88 eeeeee-eeeee eeeeee eee e 8-M eeeeee (88-ee eeee eee 88-ee ee eeeeeeee) eeee eeee eee eee eeeeeeeeee. Mee eeeeee ee eee MM eeeee eee e 888-M eeeeee-eeeeeeee Me eeee eee ee eeeeeeeee-eeee eeeeeeeee. M Meeee eeeeee eeeeeeee eee eeee eeeeee eee eeee ee eeeeee eee eeeeeeeeeee eeeee 888ee. Meee eeeee eee eeeeeee eeee eeeeeeeeeeeeeeeee (888; 888ee, 8.88eeee) eee eeeeee eeeee eeeeeee eeeeeeee ee eeeee eeeee eeeeee ee e eee eee/eeeeeee eeee eeeeeeee ee eeeeeeeeee eeeeeeeeeee ee eeeeeee eeeeeeee (8.88Meee). Mee eeee eeee eee eeeeeeee ee eee eeeeee ee eee eeeeee eeeeee eeee M8M eeeeeeeeee ee 88°M. Mee eeeeee eee eeeeeeeeee ee Me eeee, eeeee eeeeee ee e eeeeeeeee. Mee eeeeee eeeeeeeeee 888 eeee eeeeee ee eee M8M ee eeeee eeeeeeeee ee eee eeee eeee eee eeeeeeeeee ee 88°M eee 88e. Meeee eeeeeeeeeee ee eee eeeeeeeeeee, eee eeeeeee eee eeeeeeeee ee eee eeeeee ee eeee eeeee ee eeeeeee eee eeeeee ee eee eeeee ee e eee eee/eeeeeee eeee, eee eee eeeee eeeeeeee eeee eeeeeeeee eeee e eeeee. Meeeeeeee ee eee 8MMMM eeeeeeee, ee eeeeeeeee ee 88% eeeeeeeeeeeeee eeee eeeeee (<8%) ee eeeeeee eee eeeeeeee eeeeeeee; eeeee: 8.88e (88%).

Meeeeeee[,8]eeee-8,8-eeeee (888, Meeeeeeeeeeeee):[‌888‌]

Meeeeeeeeee Meeeee: Mee eeeeeeeeee eee ee eeeeeee eee ee e Meeeeee eeeeeeeee eeeeeeee eeee 88 MMM 8888-M eeeee. M eeeeeeeeeee Meeee eeeeee, 88-ee eeee eee 88-ee ee eeeeeeee, eeeeeeeee eeee e 88-ee eeee eeeeee ee eee eeeeee eee e eeeee eeeee ee eee eeeee eee, eee eeeeeeee eee eee eeeeeeeeee. M eeeeee ee eeeeeeeeeeeeeeeee (888; 8.88e, 8.8eeee) eee eeeee ee eee eeee eeeeee. Mee eeeeee eee eeeeee eeee e eee eee/eeeeeee eeee, eee eee eeeeee eee eeeeee eeeee eeeeeee eeeeeeee (8.88Meee). Mee eeeeee eee eeeeeeeeee ee eee eeeeee ee eee Meeeeee eeeeeee, eeeee eee eeeeeee eeee Me eeee. Mee eeeeee eee eeeeeeeeee eee 88e ee eee eeeeeeeeeee eeeeeeee ee eee eeee eeeeeeeee ee eee eeeee (ee. 88°M). Meeee eeeeeeeeeee ee eee eeeeeeeeeee, eee eeeeeee eee eeeeeeeee eeee eee eeee eeeeee ee eeeeeeeeeee ee e eee eee/eeeeeee eeee; eee eeee eeeeee eee eeee eeeeeeee eeee eee eeeeeeee eeeeee. Mee eeeeeee eeeeeeeee ee >88% eeeeeeeeeeeeee, eeee eeeeee ee eeeeeee (<8%) eee 888 (<8%); eeeee: 8.88e (88%); 8MMMM (MMe8, δ): 8.88 (e, 8M), 8.88 (e, 8M), 8.88 (e, 8M).