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Volumn 14, Issue 6, 2010, Pages 1427-1431

Practical access to metallo thiophenes: Regioselective synthesis of 2,4-disubstituted thiophenes

Author keywords

[No Author keywords available]

Indexed keywords

AGE EFFECTS; CHEMO-SELECTIVITY; CRYOGENIC CONDITIONS; FUNCTIONALIZATIONS; GRIGNARD REAGENT; IN-SITU; METALATIONS; METHYLTHIOPHENE; PHTHALAZINONE; PHTHALIC ANHYDRIDES; PROLONGED REACTION; REGIOSELECTIVE MAGNESIATION; REGIOSELECTIVE SYNTHESIS; TRANSMETALATION;

EID: 78649651002     PISSN: 10836160     EISSN: 1520586X     Source Type: Journal    
DOI: 10.1021/op100226k     Document Type: Article
Times cited : (10)

References (37)
  • 11
    • 78649640494 scopus 로고    scopus 로고
    • Regioisomeric ratio upon reaction with phthalic anhydride (not a direct measurement of deprotonation)
    • Regioisomeric ratio upon reaction with phthalic anhydride (not a direct measurement of deprotonation).
  • 12
    • 78649649320 scopus 로고    scopus 로고
    • 13C NMR indicates that isolated keto acid 4 exists as the open form shown in Scheme 2 and side product 5 exists as the closed lactone form
    • 13C NMR indicates that isolated keto acid 4 exists as the open form shown in Scheme 2 and side product 5 exists as the closed lactone form.
  • 14
    • 78649673194 scopus 로고    scopus 로고
    • Using the solvent DME resulted in a 1:1.4 ratio of 4: 5, possibly indicating a destabilization of alkoxide 7b
    • Using the solvent DME resulted in a 1:1.4 ratio of 4: 5, possibly indicating a destabilization of alkoxide 7b.
  • 22
    • 78649667243 scopus 로고    scopus 로고
    • For a relevant discussion, see
    • For a relevant discussion, see
  • 24
    • 78649638114 scopus 로고    scopus 로고
    • 3OD, indicating competitive electrophilic iodination of the Me-substituted alkene
    • 3OD, indicating competitive electrophilic iodination of the Me-substituted alkene.
  • 25
    • 78649677732 scopus 로고    scopus 로고
    • No change in rate was observed with i PrMgCl.LiCl instead of i -PrMgCl
    • No change in rate was observed with i PrMgCl.LiCl instead of i -PrMgCl.
  • 26
    • 78649659611 scopus 로고    scopus 로고
    • Residual n -hexane complicated the through-process synthesis of phthalazinone 6 (oiling during crystallization) and was abandoned for the synthesis of this particular target. Further investigation of n -hexylmagnesium chloride in similar applications is underway
    • Residual n -hexane complicated the through-process synthesis of phthalazinone 6 (oiling during crystallization) and was abandoned for the synthesis of this particular target. Further investigation of n -hexylmagnesium chloride in similar applications is underway.
  • 27
    • 78649658467 scopus 로고    scopus 로고
    • For reversible metalation of other heterocycles, see
    • For reversible metalation of other heterocycles, see
  • 31
    • 78649649319 scopus 로고    scopus 로고
    • Use of excess i -PrMgCl (≥1.3 equiv) is detrimental to phthalic anhydride addition, producing a side product from isopropyl incorporation into keto acid product 4
    • Use of excess i -PrMgCl (≥1.3 equiv) is detrimental to phthalic anhydride addition, producing a side product from isopropyl incorporation into keto acid product 4.
  • 32
    • 78649639126 scopus 로고    scopus 로고
    • Magnesium or lithium aggregates have been implicated in reversible metallations of this type. See references 16a-16c and references within for more details
    • Magnesium or lithium aggregates have been implicated in reversible metallations of this type. See references 16a-16c and references within for more details.
  • 33
    • 78649666722 scopus 로고    scopus 로고
    • The 98% conversion is calculated on the basis of the limiting reagent i -PrMgCl
    • The 98% conversion is calculated on the basis of the limiting reagent i -PrMgCl.
  • 34
    • 78649645313 scopus 로고    scopus 로고
    • Yield and equivalents are based on the limiting reagent phthalic anhydride
    • Yield and equivalents are based on the limiting reagent phthalic anhydride.
  • 35
    • 0028088049 scopus 로고
    • See Supporting Information for a detailed procedure
    • Lin, H.-S.; Paquette, L. A. Synth. Commun. 1994, 24, 2503-2506. See Supporting Information for a detailed procedure
    • (1994) Synth. Commun. , vol.24 , pp. 2503-2506
    • Lin, H.-S.1    Paquette, L.A.2
  • 36
    • 78649663341 scopus 로고    scopus 로고
    • In a power compensation calorimetry experiment conducted at 10°C isothermal, quenching the reaction with water (4 volumes over 1 h, 60.6 mmol scale) resulted in a 74 kJ/mol exotherm, uncorrected for heat of mixing
    • In a power compensation calorimetry experiment conducted at 10°C isothermal, quenching the reaction with water (4 volumes over 1 h, 60.6 mmol scale) resulted in a 74 kJ/mol exotherm, uncorrected for heat of mixing.
  • 37
    • 78649640493 scopus 로고    scopus 로고
    • This reaction proceeds below the flash point of 35% hydrazine/water (112.7°C) and below the boiling point of a hydrazine/water azeotrope (120.3°C). DSC and ARC scanning of the reaction components at 300 and 250°C, respectively, showed no unsafe thermodynamic events
    • This reaction proceeds below the flash point of 35% hydrazine/water (112.7°C) and below the boiling point of a hydrazine/water azeotrope (120.3°C). DSC and ARC scanning of the reaction components at 300 and 250°C, respectively, showed no unsafe thermodynamic events.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.