TMG catalyzed cyclopropanation of cyclopentenone. Illustration by a simple synthesis of bicyclo[3.1.0]hexane-2-one derivatives

Tetrahedron Letters

Volumn 48, Issue 18, 2007, Pages 3277-3279

  Zhang, Fuyao ^a   Moher, Eric D ^a   Zhang, Tony Y ^a  

^a ELI LILLY AND COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1,1,3,3 TETRAMETHYLGUANIDINE; GUANIDINE DERIVATIVE; HEXANE; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CYCLOPROPANATION; STEREOCHEMISTRY; SYNTHESIS;

EID: 34047119071     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2007.03.006     Document Type: Article

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13. 3) δ 212.2, 170.9, 61.6, 32.4, 29.6, 26.9, 23.0, 14.7.
14. The price of TMG ($3.80/mol) is lower than DBU ($4.20/mol) in ton quantity.
15. Recovery of TMG: 23.5 g of white solid (TMG HBr salt) in a 500 mL of separation funnel was treated with 100 mL of 50% NaOH aqueous solution. The generated TMG was extracted with methylene chloride (3 × 200 mL). The combined methylene chloride solutions were dried over sodium sulfate and evaporated to provide 11.7 g (85% recovery) of 1,1,3,3-tetramethylguanidine (TMG).
16. TMG can also be recovered by extraction with toluene (75% recovery) and isopropyl acetate (71% recovery).
17. 3) δ 212.2, 170. 9, 61.6, 32.4, 29.6, 26.9, 23.0, 14.7.
18. Cyclopropanation of 2-cyclohexen-1-one was carried out under the same condition to give the bicyclo[4.1.0] adduct 5 in 59% yield and 99% dr{A figure is presented}.
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22. 3) δ 209.9, 169.7, 68.4, 61.9, 42.9, 36.5, 34.5, 25.7, 14.3.