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17.4.2.4.1.3.1.3 Variation 3: Of Hydroxy Groups

DOI: 10.1055/sos-SD-017-00991

von Angerer, S.Science of Synthesis, (200417691.

Pharmaceutical interest in dibenz[b,f]oxepins 173 with various side chains at C10(11) has stimulated a search for a convenient method for the introduction of functional groups at this position. One such approach requires O-protonation of the carbonyl group of a dibenz[b,f]oxepin-10(11H)-one 171, followed by a formal displacement of the hydroxy group of the intermediate enol (or its equivalent) 172 by a nucleophile. Suitable nucleophiles are amines or thiols, and the Lewis acids boron trifluoridediethyl ether complex or titanium tetrachloride can be used as catalysts in the first step of the procedure (Scheme 60).[‌16‌,‌20‌,‌80‌,‌82‌,‌123‌,‌137‌,‌138‌]

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M8 M8 M8 Me Meeeeeeeee Meeeee (%) ee 888 eee (°M) Mee
M M M MMM8MM8MMe8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888e [‌88‌]
M M M MMM8MM8MMe8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888e [‌88‌]
M M M MMM8MM8M(eMe)8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 8888e [‌88‌]
M M M MMM8MM8MMMM8Mee MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888e [‌88‌]
M M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee ee eeeeeee, M8, eeeeee e.e. 888888e [‌88‌,‌88‌]
M M M MMM8MM8M MeMM, MM8MMe8, 88°M e.e. e.e. [‌888‌]
M M M MMM8MM8MMe8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888e [‌88‌]
M M M 8-eeeeeeeeeeeeeee-8-ee MeMM, eeeeeee, eeeeee e.e. 888888 (eee.) [‌888‌]
M M MMe MMM8MM8MMe8e MeMM, MM8MMe8, 88°M, 88e 88 888888e [‌88‌]
M MMe M MMM8MM8MMe8e MeMM, MM8MMe8, 88°M, 88e 88 888888e [‌88‌]
M Me M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, M8, eeeeee, 8e 88 888888e [‌88‌]
Me M M eeeeeeeee-8-ee MeMe8, eeeeeee, ee, 8e, eeeeee, 88e e.e. 888888.8e [‌888‌]
Me M M 8-eeeeeeeeeeeeeee-8-ee MeMM, eeeeeee, eeeeee, 88e 88 e.e. [‌888‌]
Me M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, M8, eeeeee, 8e 88 888888e [‌88‌]
Me M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e e.e. 888e [‌88‌]
Me M M 8-(eeee-8-eeee)eeeeeeeee-8-ee MeMe8, eeeeeee, ee, 8e, eeeeee, 88e e.e. 888888e [‌888‌]
Me M M 8-(8-eeeeeeeeeeeee)eeeeeeeee-8-ee MeMe8, eeeeeee, ee, 8e, eeeeee, 88e e.e. 888888 [‌888‌]
Me M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, ee, 8e, eeeeee, 88e e.e. 888888 [‌888‌]
Me M M MMM8MM8MMe8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888 [‌88‌]
Me M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e 88 888888 [‌88‌,‌888‌]
MMe M M eeeeeeeee-8-ee MeMe8, eeeeeee, ee, 8e, eeeeee, 88e e.e. 888888.8e [‌888‌]
MMe M M 8-eeeeeeeeeeeeeee-8-ee MeMM, eeeeeee, eeeeee e.e. 888888e [‌888‌,‌888‌]
MMe M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e 88 888888e [‌88‌]
MMe M M MMM8MM8MMe8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888e [‌88‌]
MMe M M MMM8MM8MMe8e MeMM, MM8MMe8, ee, 88e, eeeeee, 88eee 88 888888e [‌88‌]
MMe M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e 88 888888e [‌88‌,‌888‌]
Me M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e 88 888888e [‌88‌,‌888‌]
MM8 M M eeeeeeeee-8-ee MeMe8, eeeeeee, ee, 8e, eeeeee, 88e e.e. 888888e [‌888‌]
MM8 M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e 88 888888 [‌88‌,‌888‌]
MM8MMe8 M M 8-eeeeeeeeeeeeeee-8-ee MeMe8, eeeeeee, 888°M, 8e 88 888888e [‌88‌,‌888‌]

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e Meeeeee eeee, eeee MeMM/Me8M.

e Meeeeee eeee, eeee eeeeeee/Me8M.

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e Meeeeee eeee, eeee eeeeeee/MeMM/Me8M.

e Meee eMeMM.

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e Meee eMe8M.

Meeeeeeeeeee Meeeeeeeee

8-Meeeee-88-(8-eeeeeeeeeeeeeee-8-ee)eeeeee[e,e]eeeeee (888, M8=M8=M; M8=Me; Me=M8M8M8Me):[‌88‌]

M eeee ee M-eeeeeeeeeeeeeeee (8.88e, 88eeee) ee eee eeeeeee (88eM) (MMMMMMM: eeeeeeeeee) eee eeeeee eeeee eeeee M8 ee e eeee ee 8-eeeeeeeeeeee[e,e]eeeeee-88(88M)-eee (888; 8.88e, 8.8eeee) eee MeMe8 (8.8e, 8.8eeee) ee eee eeeeeee (88eM) ee ee, eee eee eeeeeee eee eeeeee eee 8e. Meeee eeeeeee, eee. ee Me8MM8 eeee (88eM) eee eeeee, eee eee eeeeeee eee eeeeeee eeeeeeeee eee eeee eeeeeeee ee eeeeee eeeee MeM8. Mee eeeeee eeee eee eeeeee eeee Me8M, eee eee eeeeeeee eee eeeeeeee eeee eeeeeeee eee eeee eeeeeeeee. Mee eeeeeee eeeee eee eeeeeeeee eeee Me8M, eee eee Me8M eeeeeee eee eeeee ee eee eeeeeee/Me8M eeeeeeee. Meee eeeeeee eee eeeee (Me8MM8) eee eeeeeeeeee. Meeeeeeeeeeeeee ee eee eeeee eeeeeee (eMe8M) eeee eee eeeee eeeeeeee; eeeee: 8.8e (88%); ee 888888°M.

88-{[8-(Meeeeeeeeeeee)eeeee]eeeeeeee}eeeeee[e,e]eeeeee Meeeeee (888, M8=M 8=M8=M; Me=MMM8MM8MMe8):[‌88‌]

M eeeeeee ee eeeeee[e,e]eeeeee-88(88M)-eee (888; 8.8e, 8.8eeee) eee 8-(eeeeeeeeeeeee)eeeeeeeeeee eeeeeeeeeeeee ee eeeeeee MeMM (88eM) eeeeeeeeee MM8MMe8 (8eM) eee eeeeeee ee ee eee 88e, eee eeee eeeeee ee e eeeee eeee eee 88eee. Mee eeeeee eeee eee eeee eeeeee eeee eeeeeee eee (888e) eee eee eeeeeeee, eeeeeee eeeee, ee eee eeeeeeee ee e eeeee eeeeee ee 88% ee MeMM. Mee eeeeeee eee eeee eeeeeeeee eeee Me8M, eee eee eeeeeee eee eeeeee, eeeee, eee eeeeeeeeeeee ee eeee e eeeeeee eee, eeeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, MeMM/MM8Me8 8:88) ee eeeeee eee eeeee eeeeeeee ee e eeeeeeeee eee; eeeee: 8.8e (88%); ee 888888°M (MeMM/Me8M).

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