Two Protocols for the Conversion of Biphenol to Binaphthol: Synthesis of Diospyrol

Abstract

The application of directed orthometallation (DoM), Fries rearrangement and transmetallation followed by allylation and cyclization is reported for the conversion of biphenol to binaphthol as a means for the synthesis of diospyrol. Furthermore, the same transformation can be accomplished by the reaction of the dienolate anion of an α,β-unsaturated amide with an aryne intermediate.

arynes - biaryls - ring closure - directed orthometallation - Fries rearrangement

References and Notes

<A NAME="RD19405ST-1A">1a</A> Snieckus V. Chem. Rev.  1990,  90:  879 

<A NAME="RD19405ST-1B">1b</A> Green L. Chauder B. Snieckus V. J. Heterocycl. Chem.  1999,  36:  1453 

<A NAME="RD19405ST-1C">1c</A> Chauder B. Green L. Snieckus V. Pure Appl. Chem.  1999,  71:  1521 

<A NAME="RD19405ST-1D">1d</A> Whisler MC. MacNeil S. Snieckus V. Beak P. Angew. Chem. Int. Ed.  2004,  43:  2006 

<A NAME="RD19405ST-2">2</A> Clayden J. Organolithiums: Selectivity for Synthesis   Vol. 23:  Baldwin JE. Williams RM. Tetrahedron Organic Chemistry Series, Pergamon Press; Oxford: 2002. 

<A NAME="RD19405ST-3">3</A> Gilman H. Bebb RL. J. Am. Chem. Soc.  1939,  61:  109 

<A NAME="RD19405ST-4">4</A> Wittig G. Fuhrmann G. Chem. Ber.  1940,  73:  1197 

<A NAME="RD19405ST-5A">5a</A> Loder JW. Mongkolsuk S. Robertson A. Whalley WB. J. Chem. Soc.  1957,  2233 

<A NAME="RD19405ST-5B">5b</A> Mongkolsuk S. Sdarwonvivat C. J. Chem. Soc.  1965,  1533 

<A NAME="RD19405ST-5C">5c</A> Yoshihira K. Natori S. Kanchanapee P. Tetrahedron Lett.  1967,  4857 

<A NAME="RD19405ST-5D">5d</A> Yoshihira K. Tezuka M. Kanchanapee P. Natori S. Chem. Pharm. Bull.  1971,  19:  2271 

<A NAME="RD19405ST-5E">5e</A> Borsub L. Thebtaranonth Y. Ruchirawat S. Sadavongvivad C. Tetrahedron Lett.  1976,  105 

<A NAME="RD19405ST-6A">6a</A> Daengsvang S. Mangalasmaya M. Ann. Trop. Med. Parasitol.  1941,  35:  43 

<A NAME="RD19405ST-6B">6b</A> Sadun EH. Vajrasthira S. J. Parasitol.  1954,  40:  49 

<A NAME="RD19405ST-7A">7a</A> Manfredi KP. Blunt JW. Cardellina JH. McMahon JB. Pannell LL. Cragg GM. Boyd MR. J. Med. Chem.  1991,  34:  3402 

<A NAME="RD19405ST-7B">7b</A> Hallock YF. Manfredi KP. Dai J.-R. Cardellina JH. Gulakowski RJ. McMahon JB. Schäffer M. Stahl M. Gulden K.-P. Bringmann G. François G. Boyd MR. J. Nat. Prod.  1997,  60:  677 

<A NAME="RD19405ST-8">8</A> Boyd MR. Hallock YF. Cardellina JH. Manfredi KP. Blunt JW. McMahon JB. Buckheit RW. Bringmann G. Schäffer M. Cragg GM. Thomas DW. Jato JG. J. Med. Chem.  1994,  37:  1740 

<A NAME="RD19405ST-9A">9a</A> Sahakitpichan P. Thasana N. Ruchirawat S. Synthesis  2005,  2934 

<A NAME="RD19405ST-9B">9b</A> Govindachari TR. Viswanathan N. Ravindranath KR. Anjaneyulu B. Indian J. Chem.  1973,  11:  1081 

<A NAME="RD19405ST-9C">9c</A> Mahidol C. Tarnchompoo B. Thebtaranonth C. Thebtaranonth Y. Tetrahedron Lett.  1989,  30:  3861 

For the synthesis of naphthol derivatives via regiospecific aryne annulation, see:

<A NAME="RD19405ST-10A">10a</A> Hoye TR. Chen M. Mi L. Priest OP. Tetrahedron Lett.  1994,  35:  8747 

<A NAME="RD19405ST-10B">10b</A> Hoye TR. Mi L. Tetrahedron Lett.  1996,  37:  3097 

<A NAME="RD19405ST-10C">10c</A> Hoye TR. Mi L. J. Org. Chem.  1997,  62:  8586 

<A NAME="RD19405ST-10D">10d</A> Hoye TR. Chen M. Hoang B. Mi L. Priest OP. J. Org. Chem.  1999,  64:  7184 

<A NAME="RD19405ST-11A">11a</A> Beak P. Brown RA. J. Org. Chem.  1977,  42:  1823 

<A NAME="RD19405ST-11B">11b</A> de Silva SO. Reed JN. Snieckus V. Tetrahedron Lett.  1978,  5099 

<A NAME="RD19405ST-11C">11c</A> Beak P. Brown RA. J. Org. Chem.  1979,  44:  4463 

<A NAME="RD19405ST-11D">11d</A> Meyers AI. Lutomski K. J. Org. Chem.  1979,  44:  4464 

<A NAME="RD19405ST-11E">11e</A> Sibi MP. Jalil Miah MA. Snieckus V. J. Org. Chem.  1984,  49:  737 

<A NAME="RD19405ST-12A">12a</A> Sibi MP. Snieckus V. J. Org. Chem.  1983,  48:  1935 

<A NAME="RD19405ST-12B">12b</A> Sibi MP. Chattopadhyay S. Dankwardt JW. Snieckus V. J. Am. Chem. Soc.  1985,  107:  6312 

<A NAME="RD19405ST-12C">12c</A> Parsons AS. Garcia JM. Snieckus V. Tetrahedron Lett.  1994,  35:  7537 

<A NAME="RD19405ST-12D">12d</A> Blakemore PR. Kilner C. Milicevic SD. J. Org. Chem.  2005,  70:  373 

<A NAME="RD19405ST-13A">13a</A> Casas R. Cavé C. d’Angelo J. Tetrahedron Lett.  1995,  36:  1039 

<A NAME="RD19405ST-13B">13b</A> Superchi S. Minutolo F. Pini D. Salvadori P. J. Org. Chem.  1996,  61:  3183 

<A NAME="RD19405ST-13C">13c</A> Fürstner A. Seidel G. Kindler N. Tetrahedron  1999,  55:  8215 

<A NAME="RD19405ST-14">14</A>

Directed Orthometallation (DoM) and Fries Rearrangement.
To a solution t-BuLi (1.7 M, 30 mL, 50 mmol) and TMEDA (7.5 mL, 50 mmol) in dry THF (100 mL) was slowly added a solution of 2,2′-N,N-diethylcarbamoyl-1,1′-biphenyl (10, 7.68 g, 20 mmol) in THF (50 mL) at -78 °C under N₂ atmosphere. The stirred reaction mixture was allowed to attain r.t. overnight and treated with a sat. NH₄Cl solution. The organic solvent was removed in vacuo and the remaining solution was extracted with CH₂Cl₂. The combined organic layer was washed with H₂O, brine, dried (anhyd Na₂SO₄), and evaporated to give a viscous oil. After purification by flash column chromatography using EtOAc-hexane as eluent, 2,2′-dihydroxybiphenyl-3,3′-dicarboxylic acid bisdiethyl amide(4) was obtained (6.14 g, 80%) as a white solid; mp 140-141 °C (EtOAc-hexane). IR (KBr): 3428, 2981, 1600, 1572, 1488, 1450, 1408, 1353, 1311, 1259, 1141 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 1.27 (t, J = 7.0 Hz, 12 H), 3.53 (q, J = 7.0 Hz, 8 H), 6.99 (t, J = 7.2, 7.8 Hz, 2 H), 7.31 (dd, J = 1.8, 7.8 Hz, 2 H), 7.38 (dd, J = 2.0, 7.7 Hz, 2 H). ¹³C NMR (50 MHz, CDCl₃): δ = 13.4, 41.2, 119.3, 120.8, 127.1, 127.2, 133.7, 149.0, 171.0. MS (EI): m/z (%) = 385 (20) [M⁺ + 1], 384 (72) [M⁺], 383 (51), 313 (78), 312 (46), 311 (82), 310 (45), 295 (21), 285 (72), 283 (38), 240 (27), 239 (100). HRMS (FAB): m/z calcd for C₂₂H₂₈N₂O₄ [M + H⁺]: 385.2127; found: 385.2128.

<A NAME="RD19405ST-15">15</A>

Yield of 3b was improved to 53% using CuBr·SMe₂.

For intramolecular cyclization of allylbenzamide derivatives, see:

<A NAME="RD19405ST-16A">16a</A> Yu S. Rabalakos C. Mitchell WD. Wulff WD. Org. Lett.  2005,  7:  367 

<A NAME="RD19405ST-16B">16b</A> de Koning CB. Michael JP. Rousseau AL. J. Chem. Soc., Perkin Trans. 1  2000,  787 

<A NAME="RD19405ST-16C">16c</A> de Koning CB. Michael JP. Rousseau AL. Tetrahedron Lett.  1997,  38:  893 

<A NAME="RD19405ST-16D">16d</A> Sibi MP. Dankwardt JW. Snieckus V. J. Org. Chem.  1986,  51:  271 

<A NAME="RD19405ST-16E">16e</A> Hattori T. Takeda A. Suzuki K. Koike N. Koshiishi E. Miyano S. J. Chem. Soc., Perkin Trans. 1  1998,  3661 

<A NAME="RD19405ST-16F">16f</A> Namsaaid A. Ruchirawat S. Org. Lett.  2002,  4:  2633 

<A NAME="RD19405ST-17">17</A>

Representative Procedure for the Double Ring Closure.
To a stirred THF (5 mL) solution of 2,2′-dimethoxy-4,4′-bis(2-methylallyl)biphenyl-3,3′-dicarboxylic acid bisdiethyl amide (3a, 0.1316 g, 0.25 mmol) at -78 °C under Ar was added a solution of MeLi (1.4 M, 1.1 mL, 1.5 mmol) in Et₂O. The solution turned deep violet and was allowed to warm to r.t. and stirred at this temperature overnight. The reaction was quenched by the addition of 20 mL of sat. NH₄Cl and extracted with CH₂Cl₂. The organic layer was combined, washed with H₂O, brine and dried (anhyd Na₂SO₄). The crude product obtained after evaporation of CH₂Cl₂ was purified by PLC using CH₂Cl₂-hexane (2:1) as eluent to give white solid as 1,1′-dimethoxy-6,6′-dimethyl-2,2′-binaph-thalenyl-8,8-diol (1a, 0.0699 g, 75%); mp 234-236 °C (EtOAc-hexane). IR (KBr): 3321, 2926, 1637, 1573, 1460, 1378, 1354, 1058 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.47 (s, 6 H), 3.58 (s, 6 H), 6.82 (d, J = 1.4 Hz, 2 H), 7.17 (br s, 2 H), 7.50 (d, J = 8.5 Hz, 2 H), 7.58 (d, J = 8.5 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.7, 61.8, 112.9, 115.5, 118.4, 123.7, 124.3, 129.1, 136.5, 138.7, 153.4, 154.1. MS (EI): m/z (%) = 374 (61) [M⁺], 356 (15), 343 (23), 342 (81), 329 (36), 328 (100). HRMS (micro-TOF, ESI): m/z calcd for C₂₄H₂₂O₄ [M + H⁺]: 375.1591; found: 375.1584.

<A NAME="RD19405ST-18A">18a</A> Charette AB. Chua P. Synlett  1998,  163 

<A NAME="RD19405ST-18B">18b</A> Charette AB. Grenon M. Tetrahedron Lett.  2000,  41:  1677 

<A NAME="RD19405ST-19">19</A>

Representative Procedure for the Aryne Annulation. A solution of lithium 2,2,6,6-tetramethylpiperidine (LTMP, 6.4 mmol) was prepared at 0 °C from 2,2,6,6-tetramethyl-piperidine (1.1 mL) and n-BuLi (4.95 mL) in dry THF (20 mL). After 30 min, the solution was cooled to -78 °C and a solution of N,N-diethyl seneciomide (7a, 0.66 g, 4.3 mmol) in dry THF (5 mL) was added and stirred at this temperature for 1 h. A solution of tetrabromo-2,2′-dimethoxybiphenyl (6, 0.57 g, 1.1 mmol) in dry THF (15 mL) was added drop-wise, the reaction turned to dark red. After the addition was complete, the reaction was slowly warmed to r.t. and stirred overnight. Then, sat. NH₄Cl was added and the mixture was extracted with CH₂Cl₂. The combined organic layer was washed with H₂O, brine and dried (Na₂SO₄) and evaporated to dryness. Further purification was carried out by PLC (SiO₂, 4% EtOAc-hexane) to obtain binaphthol 12 (0.117 g, 20%).
Compound 12: mp 249-250 °C (EtOAc-hexane). IR (CHCl₃): 3344 (OH), 3010, 1636, 1369, 803 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 2.55 (s, 6 H), 3.61 (s, 6 H), 6.91 (d, J = 1.3 Hz, 2 H), 7.56 (d, J = 0.9 Hz, 2 H), 7.84 (s, 2 H), 9.76 (s, 2 H). ¹³C NMR (50 MHz, CDCl₃): δ = 22.0, 62.3, 114.3, 116.3, 118.2, 118.3, 123.1, 132.1, 134.4, 140.4, 153.4, 154.4. MS (EI): m/z (%) = 534 (50) [M⁺ + 2], 532 (100) [M⁺], 530 (48), 488 (41), 486 (84), 484 (42). Anal. Calcd for C₂₄H₂₀Br₂O₄: C, 54.16; H, 3.79. Found: C, 54.27; H, 3.76.

<A NAME="RD19405ST-20">20</A> Adimurthy S. Ramachandraiah G. Tetrahedron Lett.  2004,  45:  5251 

<A NAME="RD19405ST-21">21</A> Bringmann G. Ortmann T. Feineis D. Peters E.-M. Peters K. Synthesis  2000,  383