Synthesis of Enantiopure (S,R,S)‐ and (R,S,R)‐1,4,5,8,9,16‐Hexahydroxytetraphenylenes

Abstract

Scheme 3. Synthesis of racemic 5 from 11. a) PhIA C H T U N G T R E N N U N G (OAc) 2 , CH 3 CN, H 2 O, 0 8C, 2 h, 48 % for 12, 22 % for 13; b) Zn, AcOH, room temperature, 7 h, 74 %; c) BBr 3 , CH 2 Cl 2 , 08C to room temperature, 12 h, 90 %.Scheme 4. Synthesis of (S,R,S)-5. a) CH 3 I, K 2 CO 3 , acetone, reflux, 3 h, 100 %; b) i) 2.2 equivs. BBr 3 , CH 2 Cl 2 , 08C, 15 min; ii) 2.2 equivs. Tf 2 O, pyridine, CH 2 Cl 2 , 10 h, 27 %; c) NaOH, dioxane, methanol, 60 8C, 12 h, 98 %; d) i) PhIA C H T U N G T R E N N U N G (OAc) 2 , CH 3 CN, H 2 O, 0 8C, 2 h; ii) Zn, AcOH, room temperature, 7 h, 36 %; e) BBr 3 , CH 2 Cl 2 , 08C to room temperature, 12 h, 90 % Scheme 5. Synthesis of (R,S,R)-5. a) CH 3 I, K 2 CO 3 , acetone, reflux, 3 h, 100 %; b) i) 2.2 equivs. BBr 3 , CH 2 Cl 2 , 08C, 15 min; ii) 2.2 equivs. Tf 2 O, pyridine, CH 2 Cl 2 , 10 h, 27 %; c) NaOH, dioxane, methanol, 60 8C, 12 h, 97 %; d) i) PhIA C H T U N G T R E N N U N G (OAc) 2 , CH 3 CN, H 2 O, 0 8C, 2 h; ii) Zn, AcOH, room temperature, 7 h, 34 %; e) BBr 3 , CH 2 Cl 2 , 08C to room temperature, 12 h, 92 %.

Palladium‐Catalyzed Synthesis of Heteroarene‐Fused Cyclooctatetraenes through Dehydrogenative Cyclodimerization

“…[2] Such flexible redox behavior is one of the significant characteristics of COTs, particularly those constructed from five-membered heteroaromatics where tub-to-plane interconversion of the saddle-shaped skeleton is sufficiently facilitated. [4] Owing to the unique structural and electronic properties of this class of compounds,t here exist potential applications in various fields,i ncluding asymmetric synthesis [5] and supramolecular chemistry. [4] Owing to the unique structural and electronic properties of this class of compounds,t here exist potential applications in various fields,i ncluding asymmetric synthesis [5] and supramolecular chemistry.…”

Ferrocenyl phosphane nickel carbonyls: Synthesis, solid state structure, and their use as catalysts in the oligomerization of ethylene

“…Compounds 3, 4, and 7 form centrosymmetric dimers of adjacent molecules in the solid state by p-p-interactions between one cyclopentadienyl and one phenyl (3), two cyclopentadienyl (4), or two phenyl rings (7). Geometrical details given in Figs.…”

“…Nickel phosphanes have attracted considerable interest in recent years because they can be applied successfully in homogeneous catalysis including the polymerization of formaldehyde [1,2], dimerization of propene [3][4][5][6][7][8][9][10][11], synthesis of a-olefines [12][13][14][15][16][17][18][19], asymmetric hydrocyanation of styrene [20,21], hydrogenolysis of biphenylene [22,23], and the coupling of Grignard reagents with chloropyrimidines [24,25] and aryl chlorides [26,27]. Due to their diverse applications in the field of material sciences, e.g.…”

Synthesis of tetraphenylene derivatives and their recent advances

“…Thus, conversion of racemic tetrahydroxytetraphenylene 58 into its tetra-(S)-camphorsulfonate esters after esterification with (S)-camphorsulfonyl chloride resulted in two diastereomers (132a and 132b). Chromatographic separation and subsequent deprotection afforded enantiopure 1,8,9,16-tetrahydroxyltetraphenylene (58) [79,80]. The presence of hydroxyl groups in the tetraphenylene skeleton has provided openings for further chemistry through late functional group transformations.…”

“…4) [80]. To have a better understanding of the structures of 138-140, the results of density functional theory computation showed that their structures all seemed to be rod-like chains.…”