Science of Synthesis

Black, D. A.; Fagnou, K., Science of Synthesis, (2010) 45, 606.

Intramolecular direct arylation is a valuable method for the generation of polycyclic aromatic molecules. The most common catalysts are palladium/phosphine complexes. An early report demonstrates that many different tethers (e.g., amino, ether, ketone, ester, and amide units in compound ‌154‌) can be employed in the syntheses of various polycyclic heterocycles ‌155‌, including dibenzofurans, carbazoles, and fluorenones by this approach (‌Scheme 59‌).[‌224‌,‌225‌] Phenols can be also employed as directing/activating groups for intramolecular direct arylations, as in these reactions the phenolate anion, generated in situ under the basic conditions, renders the aromatic ring more susceptible to coupling.[‌226‌] More recent advances highlight the scope and efficiency of reactions with aryl ethers that enable the synthesis of benzopyran derivatives without the need for a directing hydroxy group.[‌227‌] Dibenzo[b,d]pyran derivatives can also be synthesized through intramolecular direct arylation using a heterogeneous palladium(II) hydroxide/carbon catalyst in conjunction with a mild acetate base.[‌228‌] Other compounds that can be synthesized using intramolecular direct arylation include dibenzofurans[‌229‌] and dihydrophenanthridin-6(4H)-ones[‌230‌] (‌Scheme 59‌). Importantly, conditions are described for the use of aryl iodides, bromides, or chlorides.[‌231‌–‌233‌] The tricyclohexylphosphine ligand can be employed in the form of the corresponding phosphonium tetrafluoroborate, which makes its storage and handling more convenient.

‌Meeeee 88‌ Meeeeeeee-Meeeeeeee Meeeeeeeeeeeee Meeeee Meeeeeeee[‌888‌–‌888‌]

‌Meeeeeeeeee 88‌

e Mee ‌Meeeee 88‌ eee eeeeeeeee ee eeeeee.

e Mee ‌Meeeee 88‌ eee eeeeeeeee ee eeeeee.

Meeeeeeee-eeeeeeeee eeeeeeeee, eeeeeeee ee eeeeee eeeeeeeee, eeeeee eee eeeeeeeeeeeee ‌888‌ eee eee eeeeeeeeeeee ee ee eeeeeee eeeeeeee ee e eee-eee eeeeeee ee eeeeeeee eee eeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌] M eeeeeeee eeeeeee eee eeeeeeeeeee ‌888‌ eee eee eeeeeeeeeeeeeeeeeeeeeeeee ‌888‌ eeee eeeeeee eee eeeeeeeee ‌888‌ ee eeee eeeeeeee ee eee eeee eeeeee.[‌888‌] Meee eeeeee eeeeeee eeeeee eeeeeee eee eeeeeee eeeeeeeee ee e eeeeeee eeeeeeeeeeee (eeeeeee eeeeeeee-eeeeeeee eeee ee eeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeeeeeeee eeee eee eeeeeeeee ‌888‌), eeeee ee eeeeeee ee eee eeeee ‌888‌ eeeeee ee e eeeeeeeeeee; eeeeeeeee-eeeeeeeee eeeeee eeeeeeeee eeee eeeeeeeee eee eeeeeeeee eeeeeee ‌888‌.

‌Meeeee 88‌ Meeeeeeee Meeeeeeee Meeee Meeeee Meeeeeeeee[‌888‌,‌888‌]

Mee eee ee eeeeee ee eeeeeee eeeeeee eeeeeeeeeee eeee eeeee eee eeee eeeeeeeeeee eeeeeeee ee eee eeeeeeeee ee eeeeee-eeeeeeeeee eeeeeee eeeeeeee, ee eeeeeeeeeee ee ‌Meeeee 88‌.[‌888‌] Meee eeee eeeeeeee eee eeeeeeeeeeee ee eeeeeeeeee (‌888‌) eee eeeeeee eeeeeeeeeeeeeeeeeeee.[‌888‌] Meeeeeee’e eeeeeeee, eeeee eee ee eeeeee eeeeeeeeeee eeee eeeeeeeee(MM) eeeeeee eee eee-8-eeeeeeeeeeeeee, ee eeeeeee ee eee eeeeeeeeee ee eee ee eee eeeeee eeeeeeee ee eeeeeeeeeee (‌888‌).[‌888‌] Meeeeee Meeeeeeeeeeeee eeeeeeeee eeee ee eeeeeeeee (‌888‌) eee eeee ee eeeeeeee eeeee eee eeeeee eeeeeeeeee ee 8-eeee-8-eeeeee-8,8-eeeeeeeeeeeeee.[‌888‌] Meeeeeee eee eeeeeeeee ee eeeee-eeeeeeee ee eeeeee eeeee eeeeeee eeeeee eeeeeeeee ee eeee eeee eeeee, eee eee ee eee eeeeeeeee ‌888‌ (eee ‌Meeeee 88‌, Meeeeee ‌88.88.8.8.8‌) ee eeeeeeeeeee eeee eeeeeeeee(MM) eeeeeee ee eeeeeeee ee eeeeeeee eee eeeee ‌888‌ ee e eeee eeeeeeeeeeee eeeee. Meee eeeeeeee eee eeee ee eeeeeeeeeee eeee eeeeeeeeeeeeee (‌888‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeee, Meeeeeeeeee, Meeeeeeee, eee Meeeeeeeeeeeee[‌888‌–‌888‌]

Meee[e]eeeeeeeeeeeeeeeee ee eee eeee eeeeee eeeeeeeeeeee ee eee eeeeeeeeeeeeeeeee eeeeee, eee eee ee eeeeeeeeeeee eeeeeeeeee eeeeeeeeeeeee eeeeeeee. Meee ee eee eeeeeeeeeee, eeeeeeeee eee eeeeeeeeeeeeeee eeeeeeee ‌888‌, eee ee eeeeeeeeeee eeeeee eeeeeeeeeeeeee eeeeeeeee eeee eeeeeeee eeee (‌Meeeee 88‌).[‌888‌,‌888‌] Meee-eeeeee eeeeeeee eeeeeeeee eee eeee ee eeeeeeee eee ee eeeee eeeeeeeeee ee eeeeeeeeee, ee eeee eeeeeee eeee eeeeee eee eeeeeee π-eeeeeeee, ee eeee ee eeee eeeeeee ee eeeeee eeeeee eeeeeeeeee eeee eee eeeeeeeeeee eeee eeeeeeee ee8 eeeeeee. Meeeeeeeeeee eee eeeeeeeee, eeee ee eeeeeeeeee[8,8,8,8-eeeee]eeeeee (‌888‌) eee 88-eeee-eeeee-8e,8,88,88e-eeeeeeeeee-8eM-eeeeeeeeee[eee]eeeeee[8,8,8,8-eeee]eeeeeeee (‌888‌), eeeee eeeeeee eeeee eeeeeeee, eee eeeeeeeeeee eeeee eeeeeeeeeeeeee eeeeeeeee eeeee Meeeeeee’e eeeeeeee ee eeeeeeeeee(eeeeeeeeeeeeeeeeee)eeeeeee­ee(MM).[‌888‌–‌888‌] Meee, eeeeeeeee eeeeeeeeee eeeeeeee eeeeeee eeeeeeeee eeeeeee eeeeeeeee eeeeeeeee eee ee eeeee eeeeeeeeeeeee eeeeeee eee eeeeeeeeee eeeeeeeeee. Meeee eeeeeee eeee eeee eeeeeeee eeeeeee eee eee ee eeeeeeeee(MM) eeeeeee eee eeeeeeeeeeeeeeeeeeeeee–eeeeeeeeeeeeeeee eeee eeeeeee. Mee eeeeeee, 8,88-eeeeeeee-8,8-eeeeeeeeeeeeeeee[e,e]eeeeeeeeeeee (‌888‌) ee eeeeeeee ee eee eeeeeeeeeeeeee eeeeee eeeeeeeee ee eee eeeeeeeee ‌888‌.[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeee Meeeeeeee eee Meeeee Meeeeeeee[‌888‌–‌888‌]

Meeeee eeeeeeeee ee eeee ee eee eeeeeeeee ee eee eeeeeee eeeeeeeee ‌888‌ eee eeeeeeeeeee eeeeeee (‌Meeeee 88‌).[‌888‌,‌888‌] Meeeeeee ee eeeee eeeeeeeee ee eeeeee ee eeeee eeeeeeeee eee ee eeeeeeeeee ee eee eeeeeeeeee ee eeeeeeeeeeeeee eeeeeeeee eeeeeeeeeee, ee eeee ee ee eee eeeeeeeeeeee ee eeeeeeeee eeeee. Meeeeeeeeee-eeeee eeeeeeeee eee eeee eeeeeeeee eeeeeee e eeeeee ee eeeeee eeeeeeeeee; eee eeeeeee, eeeeeee eeeeeeee ee ee eeee eeeeeee ‌888‌, eeeeeeee ee eeeeeee eeeeeeee eeee ee eeee eeeeeeeeeeeeeeeeeeeeeeeee eeeeeeeeee eeeeeee ee eee eeeeeeeeee ee e eeeeee eeee-eeeee eeeeeeeeeee eeeeeeeeeee ‌888‌ (‌Meeeee 88‌).[‌888‌]

‌Meeeee 88‌ Meeeeeeee ee Meeeeeeeeeeee eee Meeeee Meeeeeeeee[‌888‌–‌888‌]

Meeeeeeeeeee Meeeeeeee

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

8-Meeeeeeeeeeeeeee (8.88 e, 88 eeee), Me(MMe)8 (8.8 eeee), eee Me8M (8.8 eeee) ee 8-eeeeeeeeeeeeeee (88 eM) eeee eeeeee eeeee M8 ee 888°M eee 8.8 e. Mee eeeeeee eee eeee eeeeee ee ee eee eeeeee eeee M8M, eeeeee ee eee eeeeeeeee eeee eeeeeee. Mee eeeeeee eee eeeeeeeeeeee eeeeeee eeee eee eeeeeeee eeeeeeee eeeee eeeeeee eeeeeeee; eeeee: 8.8 e (888%).

8M-Meeeeee[e,e]eeeee-8-eeeeeeeeeeee (‌888‌, M = MM8M; M8 = 8-MM); Meeeeee Meeeeeeee:[‌888‌]

MMMMMMM: Meeeeeeee eeeeeee eee ee eeeeee eeeeeee eee eeeeeeeeeee eeeeeeeee. Meeeeeee eeeeeeeeee ee eeeeeeeee, eeeeeeeeee eeee eee eeeeee ee eeeeee ee eee eee ee eee eeeeeeeee.

MMM (8.8 M) eee eeeee ee e eeeeeee ee MMMe (8.8 eeeee), Me(MM)8/M (8.8 eeeee), eee 8-[(8-eeeeeeeeeee)eee]eeeeeeeeeeee (8.8 eeeee), eeeeeeeee eeeee M8 eee eeee ee e 8-eM eeeee-eeeeee eeee eeeeeeee eeee e eeeeeeeeee eeeeeee eee. Mee eeeeeee eee eeee eeeeee eeeeeeeee ee 888°M, eee eeee eee eeeeeeee eee eeee (MMM ee MM/MM), eee eeee eeeeee eee eeeeeee eee eee eeeeeee eee eeeeeee ee eeee ee ee. Mee eeeee eeeeeeee eee eeeeeeee eeee eee eeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee, eeeeeee/MeMMe); eeeee: 88%; ee 88–88°M.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8e, 888.