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Synlett
Volumn , Issue 5, 2008, Pages 759-764
A Rh(I)-catalyzed cycloisomerization reaction affording cyclic trienones
Author keywords

Alkynes; Allenes; Cycloisomerization; Rh(I); Triene
Indexed keywords

2 CYCLOHEXENONE; 2 LIDENE 3 VINYCYCLOHEXENONE DERIVATIVE; 2 LIDENE 3 VINYLCYCLOPENTENONE DERIVATIVE; ALLENE DERIVATIVE; CYCLOPENTANONE DERIVATIVE; KETONE DERIVATIVE; RUTHENIUM; TRIENONE DERIVATIVE; UNCLASSIFIED DRUG;
EID: 41349121841     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1032111     Document Type: Article
Times cited : (13)
References (36)
  • 17
    • 0037042281 scopus 로고    scopus 로고
    • Metal-catalyzed carbocyclization reactions of enynones have been previously reported, for leading references, see
    • Metal-catalyzed carbocyclization reactions of enynones have been previously reported, for leading references, see: Trost, B. M.; Toste, F. D. J. Am. Chem. Soc. 2002, 124, 5025.
    • (2002) J. Am. Chem. Soc , vol.124 , pp. 5025
    • Trost, B.M.1    Toste, F.D.2
  • 18
    • 41349090979 scopus 로고    scopus 로고
    • General Procedure for the Preparation of Allene-ynones 3 (a) In a manner entirely analogous to that reported by Trost:7b A solution of the alkyne (1.08 mmol) in THF (2.4 mL) was cooled to -78°C and a solution of M-BuLi (0.6 mL of a 1.6 M solution in hexanes, 0.96 mmol) was added rapidly via syringe. After 5 min BF3·OEt2 (128 μL, 1.02 mmol) was added. The resultant solution/mixture was stirred for 15 min then a solution of the allenyl amide 1 (100 mg, 0.60 mmol) in THF (3 mL) was added via cannula. After 1.5 h, more BF3·OEt2 (128 μL, 1.02 mmol) and AcOH (58 μL, 1.02 mmol) were added. The reaction was allowed to warm to -20°C and quenched with sat. aq NH4Cl (2.1 mL, After warming to r.t, the reaction mixture was diluted with Et 2O and H2O. The layers were separated and the aqueous layer was extracted with Et2O 3x, The combined organic layers
    • +]: 254.1307; found: 254.1282.
  • 21
    • 41349109706 scopus 로고    scopus 로고
    • We have seen similarly facile reactions when the cycloisomerization substrate possesses an aminoester tether. See ref. 2c
    • We have seen similarly facile reactions when the cycloisomerization substrate possesses an aminoester tether. See ref. 2c.
  • 22
    • 0001418081 scopus 로고    scopus 로고
    • Chelation of the tethered oxygen of 3c or 3d to the Rh(I) catalyst may be responsible for the rate enhancement by facilitating the oxidative addition step of the cycloisomerization process. Trost observed a similar effect in a palladium-catalyzed enyne cycloisomerization reaction, see: Trost, B. M.; Romero, D. L.; Rise, F. J. Am. Chem. Soc. 1994, 116, 4268.
    • Chelation of the tethered oxygen of 3c or 3d to the Rh(I) catalyst may be responsible for the rate enhancement by facilitating the oxidative addition step of the cycloisomerization process. Trost observed a similar effect in a palladium-catalyzed enyne cycloisomerization reaction, see: Trost, B. M.; Romero, D. L.; Rise, F. J. Am. Chem. Soc. 1994, 116, 4268.
  • 23
    • 0027234274 scopus 로고    scopus 로고
    • Terminal ynones have been reported to undergo decomposition in palladium-catalyzed cycloisomerization reactions, see: Trost, B. M, Phan, L. T. Tetrahedron Lett. 1993, 34, 4735
    • Terminal ynones have been reported to undergo decomposition in palladium-catalyzed cycloisomerization reactions, see: Trost, B. M.; Phan, L. T. Tetrahedron Lett. 1993, 34, 4735.
  • 24
    • 41349101488 scopus 로고    scopus 로고
    • General Procedure for the Preparation of Trienone 4 A 2-dram vial, equipped with a stir bar was charged with allene-ynone 3 (0.1 mmol) and toluene (0.33 mL, sealed with a septum, and degassed (degassing was accomplished by bubbling argon through the stirred solution for 20 min, Rhodium biscarbonyl chloride dimer, Rh(CO)2Cl]2, 3 mol, was then added and the reaction progress was monitored by TLC Upon completion of the reaction, the mixture was diluted with a 10% EtOAc-hexanes solution and filtered through a pad of silica gel, further eluting with 10% EtOAc-hexanes solution. The resultant yellow solution was concentrated under vacuum to yield the products as yellow oils without further purification. Data for 4e: 1H NMR (300 MHz, CDCl3, δ, 6.27 (dd, J, 11.3, 17.7 Hz, 1 H, 6.01 (s, 1 H, 5.45 (dd, J, 2.1, 11.3 Hz, 1 H, 5.15 (dd, J, 2.1, 17.7 Hz, 1 H, 2.61-2.51 (m, 4 H, 1.95 (s, 3 H, 0.13 s, 9
    • +]: 277.1204; found: 277.1215.
  • 25
    • 41349117149 scopus 로고    scopus 로고
    • Preparation of 6,7,8,10a-Tetrahydro-2-methyl-1-vinyl-5H-xanthene (7) Following the general procedure for the preparation of trienone 4: toluene (2.8 mL, allene-ynone 3f (32 mg, 0.140 mmol, Rh(CO2)Cl]2 (1.6 mg, 0.004 mmol, 5 mol, purification by silica gel column chromatography eluting with 2% EtOAc-hexanes (column pretreated with a 1% solution of Et3N in hexanes) to afford 7 as a green solid (9 mg, 29, 1H NMR (300 MHz, CDCl3, δ, 6.85 (d, J, 8.1 Hz, 1 H, 6.63 (dd, J, 11.4, 17.8 Hz, 1 H, 6.56 (d, J, 8.1 Hz, 1 H, 6.39 (s, 1 H, 5.58 (dd, J, 2.0, 11.4 Hz, 1 H, 5.23 (dd, J, 2.0, 17.8 Hz, 1 H, 4.86 (dd, J, 5.7, 10.9 Hz, 1 H, 2.60-1.19 (m, 8 H, 2.18 (s, 3 H, 13C NMR (75 MHz, CDCl3, δ, 151.3, 137.5, 134.4, 133.7, 128.8, 127.8, 120.4, 119.1, 114.9, 113.5, 76.1, 34.7, 33.2, 26.5, 24.2, 19.8. IR thi
    • +]: 226.1358; found: 226.1353.
  • 26
    • 41349100651 scopus 로고    scopus 로고
    • Preparation of Allenyl Alkynone 9e A flame-dried 100 mL round-bottomed flask was charged with 2,2-diethylhexa-3,4-dienal (8b, 1.52 g, 10.0 mmol) and THF (40 mL, After cooling to 0°C, 1-propynylmagnesium bromide (24 mL, 0.5 M in THF, 12 mmol) was slowly added via syringe and the mixture was stirred at 0°C for 2 h. The reaction mixture was quenched with sat. NH4Cl (20 mL, The mixture was partitioned between Et2O (30 mL) and H2O (30 mL, The layers were separated and the aqueous phase was extracted with Et2O (2 x 30 mL, The combined organic layers were washed with brine, dried over MgSO4, and concentrated under reduced pressure to afford a light yellow oil (1.65 g, A portion of the oil (452 mg) was transferred into a 50 mL round-bottomed flask fitted with a Teflon-coated stirring bar and dissolved in acetone 20 mL, After cooling to 0°C, freshly prepared Jones reagent was added dropwise via a pipette unt
    • +]: 190.1357; found: 190.1358.
  • 30
    • 41349083710 scopus 로고    scopus 로고
    • Preparation of Allenyl Alkynone 11b A flame-dried 25 mL round-bottomed flask was charged with N-[2-(N-methoxy-N-methylcarbamoyl)hexa-3,4-dien-2-yl]benzamide (268 mg, 0.93 mmol) and THF (15 mL, After cooling to 0°C, 1-propynylmagnesium bromide (4.4 mL, 0.5 M in THF, 2.2 mmol) was slowly added via syringe and the mixture was stirred at 0°C for 3 h. The reaction mixture was quenched with sat. NH4Cl (10 mL, The mixture was partitioned between Et2O (15 mL) and H 2O (15 mL, The layers were separated and the aqueous phase was extracted with Et2O (2 x 15 mL, The combined organic layers were washed with brine, dried over MgSO4, and concentrated under reduced pressure to afford a white solid. The solid was purified via silica gel column chromatography (50% EtOAc-hexanes) to give the title compound 11b (242 mg, 97, as a white solid. 1H NMR (300 MHz, CDCl3, δ, 7.81-7.78 m
    • +]: 267.1259; found: 267.1263. *Denotes the minor diastereomer.
  • 31
    • 0032190825 scopus 로고    scopus 로고
    • With the exception of 12b, which had to be stored in benzene at -20°C, the only literature report on the formation of five-membered cross-conjugated triene stressed product instability. For details, see: Yamazaki, T, Urabe, H, Sato, F. Tetrahedron Lett. 1998, 39, 7333
    • With the exception of 12b, which had to be stored in benzene at -20°C, the only literature report on the formation of five-membered cross-conjugated triene stressed product instability. For details, see: Yamazaki, T.; Urabe, H.; Sato, F. Tetrahedron Lett. 1998, 39, 7333.
  • 32
    • 41349085966 scopus 로고    scopus 로고
    • General Procedure for the Preparation of Trienones 12 A flame-dried test tube equipped with a Teflon-coated stir bar was charged with allene-ynone 9 or 11 (1.0 mmol, 1 equiv) and toluene (10 mL) under an atmosphere of N2. After adding [Rh(CO)2Cl]2 (0.05 mmol, 0.05 equiv, the reaction mixture was stirred at r.t. until complete consumption of starting material (as observed by TLC, The solution was concentrated under reduced pressure and the residue was purified via silica gel column chromatography (10% EtOAc-hexanes) to afford trienone 12. Data for 12a: 1H NMR (300 MHz, CDCl3, δ, 6.44 (dd, J, 17.6, 11.1 Hz, 1 H, 6.16 (t, J, 7.4 Hz, 1 H, 6.12 (s, 1 H, 5.62 (dd, J, 17.6, 1.6 Hz, 1 H, 5.28 (dd, J, 11.1 1.6 Hz, 1 H, 2.78 (q, J, 7.5 Hz, 2 H, 1.45-1.36 (m, 4 H, 1.12 (s, 6 H, 0.92 (t, J, 6.9 Hz, 3 H, 13C NMR 75 MHz, CDCl3
    • +]: 190.1357; found: 190.1355.
  • 33
    • 41349093103 scopus 로고    scopus 로고
    • The stereochemistry has been assigned based upon X-ray crystal data of a similar compound. This information will be published in the near future
    • The stereochemistry has been assigned based upon X-ray crystal data of a similar compound. This information will be published in the near future.
  • 34
    • 41349100863 scopus 로고    scopus 로고
    • Preparation of N, 1Z,3aS,8S,8aR,8bR, 6-Ethylidene-1,2,3,3a,4,6,7,8,8a,8b-decahydro-8-methyl-1,3,7-trioxo-2- phenylcyclopenta[e]isoindol-8-yl}benzamide (13) A flame-dried test tube equipped with a Teflon-coated stirring bar was charged with N, 13Z)-4-ethylidene-1-methyl-5-oxo-3-vinylcyclopent-2-enyl] benzamide (12h, 100 mg, 0.37 mmol) and 1-phenyl-1H-pyrrole-2,5- dione (68 mg, 0.39 mmol, After adding toluene (4 mL, the test tube was placed into a preheated 80°C oil bath until complete consumption of starting materials (as observed by TLC, The solution was directly purified via silica gel column chromatography (50% EtOAc-hexanes) to afford the title compound 13 (87.4 mg, 54, 1H NMR (300 MHz, CDCl3, δ, 7.89-7.85 (m, 2 H, 7.54-7.30 (m, 7 H, 7.06-7.03 (m, 2 H, 6.70 q, J, 7.6 Hz, 1 H, 6
    • +]: 441.1814; found: 441.1812.
  • 36
    • 41349106133 scopus 로고    scopus 로고
    • Preparation of Adduct 15 To arefluxing solution of (5Z)-2,2-diethyl-5-ethylidene-4-vinylcyclopent-3-enone (12e, 28 mg, 0.15 mmol) and Rh(OAc)2 (3.3 mg, 0.0075 mmol) in CH 2Cl2 (1.5 mL) was added a CH2Cl2 (1 mL) solution of diethyl 4-diazo-2-pentenedioate (48 mg, 0.23 mmol) over 10 min under argon. After 30 min, TLC showed complete consumption of 12e. The solvent was removed and the crude mixture was purified via silica gel flash chromatography (10% EtOAc-hexanes) to give 14 (26 mg, 47, together with the trans-divinylcyclopropane (cis/trans, 7:1, A test tube was charged with 14 (19 mg, 0.051 mmol) and maleic anhydride (7.5 mg, 0.077 mmol) and purged with N2 for 5 min. Toluene (0.8 mL) was added and the test tube was placed into a preheated oil bath 80°C, After 3 h, the reaction mixture was cooled to r.t. and directly applied to silica gel flash chromatograph
    • +]: 472.2097; found: 472.2101.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.