Novel Synthetic Route to Dihydropyrenes

Kazufumi Chifuku; Tsuyoshi Sawada; Takao Kihara; Kentaro Shimojo; Hidetoshi Sonoda; Yutaka Kuwahara; Hideto Shosenji; Hirotaka Ihara

doi:10.1055/s-0028-1087363

LETTER

Novel Synthetic Route to Dihydropyrenes

Kazufumi Chifuku, Tsuyoshi Sawada*, Takao Kihara, Kentaro Shimojo, Hidetoshi Sonoda, Yutaka Kuwahara, Hideto Shosenji, Hirotaka Ihara
Department of Applied Chemistry and Biochemistry, Kumamoto University, 2-39-1 Kurokami, Kumamoto-shi, Kumamoto 860-8555, Japan
Fax: +81(96)3423679; e-Mail: sawada@gpo.kumamoto-u.ac.jp;

Abstract

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Abstract

We developed a new and short synthetic route to 2,7-di-tert-butyl-trans-15,16-dimethyldihydropyrene (DHP) via tetrahydroxy[2.2]metacyclophane in four reaction steps with a total yield of 37%. 2,7-Di-tert-butyl-trans-15,16-dimethyldihydropyrene functionalized by acetoxy groups at 4-, 5-, 9-, 10-positions was synthesized via 5,13-di-tert-butyl-8,16-dimethyl-1,2,9,10-tetrahydroxy[2.2]MCP in five reaction steps with a yield of 24%, and its DHP structure was determined by ^¹H NMR spectroscopy and X-ray crystal-structure analysis.

Key words

cyclophanes - arenes - photochemistry - reduction - oxidations

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References

References and Notes

<A NAME="RU08508ST-1">1</A> Boekelheide V. Phillips JB. J. Am. Chem. Soc. 1967, 89: 1695

<A NAME="RU08508ST-2A">2a</A> Zhao P. Fang C. Xia C. Liu D. Xie S. Chem. Phys. Lett. 2008, 453: 62

<A NAME="RU08508ST-2B">2b</A> Andreasson J. Straight SD. Bandyopadhyay S. Mitchell RH. Moore TA. Moore AL. Gust D. Angew. Chem. Int. Ed. 2007, 46: 958

<A NAME="RU08508ST-2C">2c</A> Lee H. Robinson SG. Bandyopadhyay S. Mitchell RH. Sen D. J. Mol. Biol. 2007, 371: 1163

<A NAME="RU08508ST-2D">2d</A> Straight AD. Andreasson J. Kodis G. Bandyopadhyay S. Mitchell RH. Moore TA. Moore AL. Gust D. J. Am. Chem. Soc. 2005, 127: 9403

<A NAME="RU08508ST-2E">2e</A> Liddell PA. Kodis G. Andreasson J. Garza LDL. Bandyopadhyay S. Mitchell RH. Moore TA. Moore AL. Gust D. J. Am. Chem. Soc. 2004, 126: 4803

<A NAME="RU08508ST-2F">2f</A> Marsella MJ. Wang Z. Mitchell RH. Org. Lett. 2000, 2: 2979

<A NAME="RU08508ST-3">3</A> Tashiro M. Yamato T. J. Am. Chem. Soc. 1982, 104: 3701

<A NAME="RU08508ST-4">4</A> Mitchell RH. Ward TR. Chen Y. Wang Y. Weerawarna SA. Dibble PW. Marsella MJ. Almutairi A. Wang Z. J. Am. Chem. Soc. 2003, 125: 2974

<A NAME="RU08508ST-5A">5a</A> Sahade DA. Tsukamoto K. Thiemann T. Sawada T. Mataka S. Tetrahedron 1999, 55: 2573

<A NAME="RU08508ST-5B">5b</A> Sahade DA. Mataka S. Sawada T. Tsukinoki T. Tashiro M. Tetrahedron Lett. 1997, 38: 3745

<A NAME="RU08508ST-6">6</A> Sheepwash MAL. Ward TR. Wang Y. Bandyopadhyay S. Mitchell RH. Bohne C. Photochem. Photobiol. Sci. 2003, 2: 104

<A NAME="RU08508ST-7">7</A> Zhengchun L. Classon B. J. Org. Chem. 1990, 55: 4273

Synthesis of 3 from 6
To a stirred suspension of 6 (100 mg, 0.24 mmol), imidazole (196 mg, 2.88 mmol), and chlorodiphenylphosphine (235 mg, 1.00 mol) in toluene (50 mL) was added iodine (243 mg, 1.00 mmol) portionwise at reflux temperature, and the mixture was refluxed for 1 h. Zinc powder (667 mg, 9.76 mmol) was added, and the mixture was refluxed for 8 h. The mixture was cooled to r.t. and washed with 1 M NaOH (50 mL), H₂O (50 mL), and brine. The organic layer was dried over MgSO₄, evaporated in vacuo, and purified by TLC to afford 3 (63 mg, 75%) and 7 (8 mg, 7%) as green powders.
Compound 3: mp (from n-hexane) 201-203 ˚C (lit. [4] mp 203-204 ˚C). ^¹H NMR (400 MHz, 25 ˚C, CDCl₃): δ = -4.04 (s, 6 H), 1.69 (s, 18 H), 8.46 (s, 4 H), 8.54 (s, 4 H).
Compound 7: mp (from n-hexane) 104-105 ˚C. FT-IR: 697, 732, 1026, 1109, 1130, 1161, 1236, 1360, 1437, 2861, 2906, 2926, 2967 cm^-¹. ^¹H NMR (400 MHz, 25 ˚C, CDCl₃): δ =
-4.17 (s, 3 H), -4.10 (s, 3 H), 1.57 (s, 9 H), 1.60 (s, 9 H), 7.27-7.39 (m, 4 H), 7.40-7.58 (m, 4 H), 8.00-8.22 (m, 2 H), 8.33 (d, J = 7.80 Hz, 1 H), 8.38 (d, J = 7.84 Hz, 1 H), 8.43 (s. 1 H), 8.45 (s, 1 H), 8.49 (s, 1 H), 8.67 (s, 1 H), 8.82 (s, 1 H). ^¹³C NMR (100 MHz, 25 ˚C, CDCl₃): δ = 29.53, 29.68, 31.81, 31.86, 31.89, 31.96, 36.00, 36.03, 115.85, 120.48, 121.04, 121.59, 122.50, 122.80, 123.26, 124.51, 128.39, 128.70, 131.80, 132.26, 135.14, 136.54, 137.47, 142.10, 144,59, 146.91. HRMS-FAB⁺: m/z calcd for C₃₈H₄₁O₂P + Na: 583.2775; found: 583.2776 [M⁺ + Na].

<A NAME="RU08508ST-9">9</A> Garegg PJ. Samuelsson B. Synthesis 1979, 469

<A NAME="RU08508ST-10">10</A> Fox DJ. Pedersen DS. Petersen AB. Warren S. Org. Biomol. Chem. 2006, 4: 3117

<A NAME="RU08508ST-11">11</A> Tsukamoto K. Sahade DA. Taniguchi M. Sawada T. Thiemann T. Mataka S. Tetrahedron Lett. 1999, 40: 4691

<A NAME="RU08508ST-12">12</A> Albright JD. Goldman L. J. Am. Chem. Soc. 1967, 89: 2416

Oxidation of 6 to 11
A solution of 6 (1.00 g, 2.40 mmol) in DMSO (100 mL) was degassed in vacuo, Ac₂O (10.0 ml, 97.2 mmol) was added, and the mixture was degassed in vacuo. The reaction mixture was stirred for 20 h under nitrogen at r.t. Then, H₂O (100 mL) was added and the reaction mixture was neutralized by aq NH₃. The reaction mixture was then filtered, and the precipitate was washed with H₂O and cold MeOH, and dried in vacuo to afford 11 (959 mg, 98%) as a yellow powder; mp 233-240 ˚C (dec.); lit [¹¹] mp 230-240 ˚C (dec.). ^¹H NMR (400 MHz, 25 ˚C, CDCl₃): δ = 0.89 (s, 6 H), 1.29 (s, 18 H), 7.58 (s, 4 H).

<A NAME="RU08508ST-14A">14a</A> Phillips KES. Katz TJ. Jockusch S. Lovinger AJ. Turro NJ. J. Am. Chem. Soc. 2001, 123: 11899

<A NAME="RU08508ST-14B">14b</A> Fox JM. Katz TJ. Van Elshocht S. Verbiest T. Kauranen M. Persoons A. Thongpanchang T. Krauss T. Brus L. J. Am. Chem. Soc. 1999, 121: 3453

Synthesis of 12 from 11
To a suspension of 11 (500 mg, 0.25 mmol) and zinc powder (1.61 g, 25.0 mmol) in dry CH₂Cl₂ (50 mL) was added Ac₂O (2.5 mL, 24.3 mmol) and Et₃N (5.0 mmol, 37.5 mmol). The mixture was stirred for 2.5 h under nitrogen at r.t., and then filtered through Celite. The filtrate was washed with 10 wt% aq HCl (50 mL) and sat. aq NaHCO₃ (50 mL). The organic layer was dried over MgSO₄ and evaporated in vacuo; the residue was recrystallized with hexane-CH₂Cl₂ to afford 12 (203 mg, 50%) as green needles.
Dihydropyrene 12: mp (from n-hexane-CH₂Cl₂): 257-258 ˚C. FT-IR: 1003, 1215, 1479, 1661, 2957, 3672 cm^-¹. ^¹H NMR (400 MHz, 25 ˚C, CDCl₃): δ = -3.28 (s, 6 H), 1.61 (s, 18 H), 2.58 (s, 12 H), 8.45 (s, 4 H). ^¹³C NMR (100 MHz, 25 ˚C, CDCl₃): δ = 20.56, 29.90, 31.05, 31.70, 36.25, 116.00, 125.75, 134.93, 147.02, 169.15. MS-FAB⁺: m/z = 576 [M⁺]. Anal. Calcd for C₃₄H₄₀O₈: C, 70.81; H, 6.99. Found: C, 70.55; H, 7.14.

<A NAME="RU08508ST-16">16</A> Chevykalova MN. Manzhukova LF. Artemova NV. Luzikov YuN. Nifant IE. Nifant EE. Russ. Chem. Bull. 2003, 52: 78

Single crystals of 12 suitable for X-ray analysis were prepared by recrystallization from CHCl₃. Diffraction data were collected on a Regaku AFC’R diffractometer at 25 ˚C with graphite monochromated Moκ_a (λ = 0.71069 Å) radiation. For structure analysis and refinement, computations were performed using the Crystal Structure crystallographic software package of Rigaku Corporation. The structure was solved by the direct method (SIR92). All nonhydrogen atoms were refined anisotropically. Hydrogen atoms were included, but not refined. The weighting scheme ω = 1/[σ^²(Fo^²) + (0.2000P)^² + 0.0000P] where P = (Fo^² - Fc^²)^². Supplementary data of 12 have been deposited with the CCDC in the CIF format (deposit No. CCDC671306).
X-ray analysis for 12: C₃₆H₄₂O₈Cl₆ (C₃₄H₄₀O₈ + 2CHCl₃)_, MW = 815.44, green needles, monoclinic, P2₁/n (# 14), Z = 2, a = 14.220 (4) Å, b = 10.2485 (19) Å, c = 14.012 (2) Å, β = 93.051 (17)˚, V = 2039.1 (7) Å^³, D _calcd = 1.328
g cm^-³, T = 298 K, µ(Moκ_a) = 4.669 cm^-¹, Rigaku AFC7R, Moκ_a (λ = 0.71069 Å), 254 parameters, R1 = 0.1193, wR2 = 0.4244, GOF = 0.901.

<A NAME="RU08508ST-18">18</A> Williams RV. Armantrout JR. Twamley B. Mitchell RH. Ward TR. Bandyopadhyay S. J. Am. Chem. Soc. 2002, 124: 13495