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DOI: 10.1055/s-0028-1083513
Synthesis of a Bicyclo[8.3.1]enediyne via Chromium-Mediated Dearomatization of 2,6-Bis(trimethylsilyl)anisole
Publication History
Publication Date:
01 October 2008 (online)
Abstract
A novel bicyclo[8.3.1]enediyne was readily synthesized by chromium-mediated dearomatization of 2,6-bis(trimethylsilyl)anisole. The enediyne undergoes Bergman cyclization with a half-life of 14.4 hours at 142 ˚C.
Key words
enediynes - dearomatization - [Cr(arene)(CO)3] complexes - Bergman cyclization - Nicholas reaction
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Nicolaou KC.Dai WM. Angew. Chem., Int. Ed. Engl. 1991, 30: 1387 - 2
Jones RR.Bergman RG. J. Am. Chem. Soc. 1972, 94: 660 - 3a
Magnus P.Carter A. J. Am. Chem. Soc. 1988, 110: 1626Reference Ris Wihthout Link - 3b
Haseltine JN.Danishefsky SJ.Schulte G.
J. Am. Chem. Soc. 1989, 111: 7638Reference Ris Wihthout Link - 3c
Mantlo NB.Danishefsky SJ. J. Org. Chem. 1989, 5: 2781Reference Ris Wihthout Link - 3d
Haseltine JN.Danishefsky SJ. J. Org. Chem. 1990, 55: 2576Reference Ris Wihthout Link - 3e
Maier E.Greiner B. Liebigs Ann. 1992, 855Reference Ris Wihthout Link - 3f
Semmelhack MF.Gallagher JJ.Minami T.Date T. J. Am. Chem. Soc. 1993, 115: 11618Reference Ris Wihthout Link - 3g
Jones GB.Fouad FS. Curr. Pharm. Des. 2002, 8: 2415Reference Ris Wihthout Link - 3h
Semmelhack MF.Wu LY.Pascal RA.Ho DM. J. Am. Chem. Soc. 2003, 125: 10496Reference Ris Wihthout Link - 4
Basak A.Mandal S.Bag SS. Chem. Rev. 2003, 103: 4077 - 5a
Maier ME.Brandstetter T. Tetrahedron Lett. 1992, 33: 7511Reference Ris Wihthout Link - 5b
Maier ME.Brandstetter T. Liebigs Ann. Chem. 1993, 1009Reference Ris Wihthout Link - 5c
Maier ME.Langenbacher D. Synlett 1994, 713Reference Ris Wihthout Link - 5d
Nishikawa T.Ino A.Isobe M. Tetrahedron 1994, 50: 1449Reference Ris Wihthout Link - 5e
Semmelhack MF.Jaskowski M.Sarpong R.Ho DM. Tetrahedron Lett. 2002, 43: 4947Reference Ris Wihthout Link - 5f
Banfi L.Basso A.Guanti G.Paravidino M.Riva R.Scapolla C. Arkivoc 2006, (vi): 15Reference Ris Wihthout Link - 5g
Banfi L.Basso A.Guanti G.Riva R. Arkivoc 2006, (vii): 261Reference Ris Wihthout Link - 6a
Nicolaou KC.Zuccarello G.Ogawa Y.Schweiger EJ.Kumazawa T. J. Am. Chem. Soc. 1988, 110: 4866Reference Ris Wihthout Link - 6b
Nicolaou KC.Sorensen EJ.Discordia R.Hwang CK.Minto RE.Bharucha KN.Bergman RG. Angew. Chem., Int. Ed. Engl. 1992, 31: 1044Reference Ris Wihthout Link - 6c
Nicolaou KC.Zuccarello G.Riemer C.Estevez VA.Dai WM. J. Am. Chem. Soc. 1992, 114: 7360Reference Ris Wihthout Link - 6d
Schreiner PR. J. Am. Chem. Soc. 1998, 120: 4184Reference Ris Wihthout Link - 7a
Magnus P.Fortt S.Pitterna T.Snyder JP. J. Am. Chem. Soc. 1990, 112: 4986Reference Ris Wihthout Link - 7b
Magnus P.Parry D.Iliadis T.Eisenbeis SA.Fairhurst RA. J. Chem. Soc., Chem. Commun. 1994, 1541Reference Ris Wihthout Link - 8a
Pape AR.Kaliappan KP.Kündig EP. Chem. Rev. 2000, 100: 2917Reference Ris Wihthout Link - 8b
Kündig EP.Pache S. In Science of Synthesis Vol. 2:Noyori R.Imamoto T. Thieme; Stuttgart: 2002. p.155-228Reference Ris Wihthout Link - 8c
Kündig EP. In Topics in Organometallic Chemistry Vol. 7: Springer; Berlin: 2004.Reference Ris Wihthout Link - 8d
Schmalz H.-G.Dehmel F. In Transition Metals for Organic Synthesis 2nd ed., Vol 1:Beller M.Bolm C. Wiley-VCH; Weinheim: 2004. p.601-617Reference Ris Wihthout Link - 8e
Kündig EP.Laxmisha MS.Cannas R.Tchertchian S.Liu RG. Helv. Chim. Acta 2005, 88: 1063Reference Ris Wihthout Link - 8f
Rosillo M.Dominguez G.Perez-Castells J. Chem. Soc. Rev. 2007, 36: 1589Reference Ris Wihthout Link - 9
Kündig EP.Sau M.Pérez-Luna A. Synlett 2006, 2114 - 10
Nicholas KM. Acc. Chem. Res. 1987, 20: 207Reference Ris Wihthout Link - 11a
Magnus P.Carter P.Elliott J.Lewis R.Harling J.Pitterna T.Bauta WE.Fortt S. J. Am. Chem. Soc. 1992, 114: 2544Reference Ris Wihthout Link - 11b
Magnus P. Tetrahedron 1994, 50: 1397Reference Ris Wihthout Link - 12
Crowther GP.Sundberg RJ.Sarpeshkar AM. J. Org: Chem. 1984, 49: 4657 - 13
Mahaffy CAL.Pauson PL. Inorg. Synth. 1979, 19: 154 - 15
Doucet H.Hierso JC. Angew. Chem. Int. Ed. 2007, 46: 834Reference Ris Wihthout Link - 16
Hamze A.Provot O.Brion JD.Alami M. J. Org. Chem. 2007, 72: 3868 - 19
O’Connor JM.Friese SJ.Rodgers BL. J. Am. Chem. Soc. 2005, 127: 16342 ; and references cited therein
References and Notes
Spectroscopic
Data
Compound
rac
-4: ¹H
NMR (400 MHz, C6D6): δ = 0.18
(d, J = 4.8
Hz, 6 H), 0.29 (s, 9 H), 0.98 (s, 9 H), 1.80 (t, J = 2.8 Hz,
1 H), 2.10 (m, 1 H), 2.25 (m, 2 H), 3.02 (dt, J = 8.8,
4.0 Hz, 1 H), 4.75 (d, J = 4.3
Hz, 1 H), 4.94 (dd, J = 10.1,
1.8 Hz, 1 H), 5.06 (d, J = 16.4
Hz, 1 H), 5.66 (ddd, J = 16.9,
9.8, 8.1 Hz, 1 H), 6.27 (d, J = 3.3
Hz, 1 H). ¹³C NMR (100 MHz, C6D6): δ = -3.8, -0.3,
18.9, 21.8, 26.6, 39.4, 43.6, 70.7, 82.7, 101.7, 115.1, 128.1, 138.4,
141.1, 152.4. IR: 3403, 2930, 2280, 1730, 1720, 1618, 1593, 1456,
1424, 1330, 1230, 4458, 1056, 1025, 768, 741 cm-¹.
MS: 347, 273, 249, 231, 217, 195, 163. HRMS: m/z calcd
for C20H35OSi2: 347.2226; found:
347.2230.
Compound
rac
-6: ¹H
NMR (400 MHz, C6D6): δ = 0.19
(dd, J = 5.0,
1.8 Hz, 6 H), 0.29 (s, 9 H), 0.98 (s, 9 H), 2.40 (m,
3
H), 3.16 (m, 1 H), 4.08 (s, 2 H), 4.79 (m, 1 H), 4.95 (d, J = 10.1 Hz,
1 H), 5.13 (d, J = 17.2
Hz, 1 H), 5.54 (m, 2 H), 5.70 (m, 1 H), 6.26 (bs, 1 H). ¹³C
NMR (100 MHz, C6D6):
δ = -3.8, -0.3,
12.3, 18.9, 23.1, 26.6, 39.7, 43.4, 46.7, 51.6, 80.8, 83.3, 95.5,
97.2, 101.7, 115.2, 118.5, 120.6, 128.7, 138.5, 141.2, 141.3, 152.5.
IR: 3420, 2954, 2928, 2214, 1623, 1572, 1473, 1407, 1361, 1330,
1245, 1203, 835 cm-¹. MS: 427, 355,
338, 279, 241. HRMS: m/z calcd
for C25H39O2Si2: 427.2483;
found: 427.2501.
Compound
rac
-8: ¹H
NMR (400 MHz, C6D6): δ = 0.24
(s, 9 H), 2.02 (m, 1 H), 2.15 (m, 1 H), 2.30 (m, 1 H), 2.74 (m,
1
H), 3.48 (m, 2 H), 3.52 (m, 1 H), 4.90 (m, 2 H), 5.28 (dt, J = 9.6, 2.8
Hz, 1 H), 5.66 (ddd, J = 17.1,
10.6, 6.6 Hz, 1 H), 6.29 (d, J = 9.9
Hz, 1 H), 6.55 (d, J = 5.3
Hz, 1 H). ¹³C NMR (100 MHz, C6D6): δ = -1.3,
26.3, 38.6, 39.5, 39.7, 52.0 109.5, 115.0, 140.1, 141.6. IR: 3585,
2953, 2089, 2050, 2016, 1639, 1601, 1426, 1316, 1277, 1246, 910,
835, 784, 760 cm-¹. MS: m/z = 598 [M + NH4
+],
581, 356, 339, 300. HRMS: m/z calcd
for C25H23O7SiCo2 [M + H+]:
580.9877; found: 580.9859.
Compound
rac
-2: ¹H
NMR (400 MHz, C6D6): δ = 0.33
(s, 9 H), 1.96 (m, 3 H), 2.35 (dd, J = 16.9,
4.3 Hz, 1 H), 2.53 (dd, J = 17.2,
4.5 Hz, 1 H), 3.21 (ddd, J = 16.9,
3.3, 2.0 Hz, 1 H), 4.12 (q, J = 8.8
Hz, 1 H), 4.84 (m, 2 H), 5.29 (m, 3 H), 6.49 (d, J = 2.8,
1 H). ¹³C NMR (100 MHz, C6D6): δ = -1.1, 23.5,
25.9, 38.2, 42.8, 46.7, 83.4, 84.2, 95.8, 97.7, 116.5, 120.8, 122.3,
140.7, 143.7, 158.3, 200,1. IR: 2280, 1656, 1611, 1450, 1328, 822
cm-¹. MS: m/z = 295,
279, 203, 190. HRMS: m/z calcd
for C19H22OSiNa [M + Na]:
317.1335; found : 317.1335.
Compound
rac
-9: ¹H
NMR (400 MHz, C6D6): δ = -0.01
(s, 9 H), 2.39 (m, 2 H), 2.69 (m, 4 H), 2.99 (dd, J = 14.3,
7.5 Hz 1 H), 4.91 (m, 2 H), 5.85 (ddd, J = 17.3,10.5,
6.4 Hz, 1 H), 6.33 (dd, J = 5.7,
1.5 Hz, 1 H), 6.68 (m, 1 H), 6.90 (m, 3 H). ¹³C
NMR (100 MHz, C6D6): δ = -1.5,
38.0, 41.0, 41.2, 47.7, 53.2, 114.8, 126.9, 128.6, 129.6, 131.2,
141.7, 156.0. IR: 2921, 1651, 1589, 1491, 1456, 1348, 1338, 1241,
1218, 1124, 985, 918, 856, 834, 744 cm-¹.
MS: m/z = 297, 283, 282.
HRMS: m/z calcd for C19H24NaOSi:
319.1488; found: 319.1491.
SPARTAN’02, Wavefunction,
Inc., Irvine, CA;
http://www.wavefun.com.
A solution of 2 (50.1 mg, 0.17 mmol) and pyrene (9 mg, 0.04 mmol) in 1,4-cyclohexadiene (5 mL) under N2 was heated in a sealed tube. After the appropriate reaction time the sealed tube was cooled in H2O and opened. An aliquot of 100 µL was removed and brought to dryness in vacuo. The solid residue was taken up in pentane (1 mL) and then analyzed by HPLC [column: SiO2 SPHERI5, solvent: hexane-i-PrOH (99:1); flow rate: 1 mL/min, detector: UV, λ = 245; sample loop: 5 µL]. The concentration of 2 and 9 was determined as the area ratio of the peaks corresponding to 2, 9, and the internal standard.