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Volumn , Issue 11, 2008, Pages 1618-1622

Conjugate allylation of cyclic α,β-unsaturated esters

Author keywords

Conjugate allylation; Cycloalkenecarboxylates; Pentalene; Regio selectivity

Indexed keywords

ALLYLLITHIUM; ALLYLTRIMETHYLSILANE; ALUMINIUM TRIS(2,6 DIPHENYLPHENOXIDE); ALUMINUM DERIVATIVE; CYCLOPENTENE DERIVATIVE; ESTER DERIVATIVE; FLUORIDE; LITHIUM DERIVATIVE; METHYLCYCLOPENTENOATE;

EID: 48549086365     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1077825     Document Type: Article
Times cited : (6)

References (68)
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    • The initial 1,2-adduct, an enone, is capable of further 1,2-addition, giving the tertiary alcohol.5
    • 5
  • 63
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    • General Procedures for the Allylation According Method B In a Schlenk flask 4 Å MS (2.00 g) and TBAF (1.31 g, 0.50 mmol) were dried under high vacuum for 30 min. Under N2 atmosphere DMF (15 mL) was added, the mixture stirred for 30 min, transferred via cannula in a Schlenk flask with 4 Å MS (2.00 g, and stirred for a further 30 min. A solution of the respective ester (1 mmol) in DMF (5 mL) was added followed by HMPA (1.04 mL, 1.07 g, 6.00 mmol) and a solution of trimethylallylsilane (0.95 mL, 685 mg, 6.00 mmol) in DMF (5 mL) at 0 °C. After stirring at 0 °C for 10 min, 1 N HC1 in MeOH (5 mL) and H2O (40 mL) were successively added, and the aqueous layer was extracted with EtOAc (2 × 100 mL, The combined organic layers were dried (MgSO4, concentrated under vacuum, and the crude product was chromatographed on SiO2 with hexanes-EtOAc. Benzyl 2-Allylcyclohexanecarboxylate (15b) Rf= 0.37
    • 2 with hexanes-EtOAc.
  • 64
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    • General Procedures for the Allylation According Method C Trimethyl aluminium (1.10 mL, 1 M in hexane, 1.10 mmol) was slowly added to a solution of 2,6-diphenylphenol (813 mg, 3.30 mmol) in toluene (6 mL) in a Schlenk flask, and the mixture stirred at r.t. for 30 min. Then a solution of the respective ester (1.00 mmol) in toluene (3 mL) was added. After 5 min, the mixture was cooled to -78 °C and stirred for 1 h. In a further flask n-BuLi (0.88 mL, 1.6 M in hexane, 1.40 mmol) was slowly added to a solution of allyltributyltin (0.43 mL, 463 mg, 1.40 mmol) in THF (4 mL) at -78 °C, and after stirring for 45 min, this allyllithium solution was transferred via cannula to the solution of the ATPH complex, and the reaction mixture stirred at -78 °C for a further 45 min. The reaction was quenched with MeOH (10 mL) and 1 N HCl (5 mL, and the aqueous layer extracted with Et2O (50 mL, The organic layer was separated, dried MgSO4z, concentrated, a
    • 2), 6.52 (dddd, J= 3.7,1.9,1.9, 0.9 Hz, 1 H, H-4′) ppm.
  • 65
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    • tert-Butyl 2-(2-Hydroxyethyl)cyclopentane-carboxylate (13) Ozone was passed through a solution of 11a (70 mg, 0.33 mmol) in MeOH-CH2Cl2-pyridine (4:4:1) at -78 °C. Then N 2 was passed for 1 min, NaBH4 (33 mg, 0.84 mmol) was added, and the reaction mixture warmed to 0 °C and stirred for 3 h. After quenching with a sat. NH4Cl soln (5 mL, the reaction mixture was extracted with EtOAc (20 mL, The combined organic layers were washed with brine (10 mL, dried (MgSO4, and concentrated under vacuum. The residue was chromatographed on SiO2 with hexanes-EtOAc (3:1, R f= 0.34) to give 13 as a colorless oil (52 mg, 74, dr 67:33, 1HNMR (500 MHz, CDCl3, δ, 1.18-1.28 (m, 1H, Ha-3, 1.45 [s, 13.5 H, C(CH3)3, C(CH 3)3*, 1.52-1.96 m, 11 H, H-l′, H*-1′, H
    • 3 [M + Na]: 237.1461; found: 237.1453.
  • 67
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    • 24
    • 24


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.