En suite generation of chromium carbonyl arene complex substituted propargylic cation and anion intermediates in side-chain functionalizations

Organometallics

Volumn 19, Issue 8, 2000, Pages 1452-1454

  Netz, Astrid ^a   Müller, Thomas J J ^a  

^a UNIVERSITY OF MUNICH   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

HARDNESS; NEGATIVE IONS; ORGANOMETALLICS; POSITIVE IONS; STABILIZERS (AGENTS);

CHROMIUM CARBONYL ARENE COMPLEX; ELECTROPHILE;

CHROMIUM COMPOUNDS;

EID: 0033750750     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om990996q     Document Type: Article

References (30)

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19. 4 (434.41): C, 69.12; H, 4.18. Found: C, 69.13; H, 4.29.
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21. tBu or LDA, suitable for the deprotonation of related toluene complexes, results only in the isolation of the isomeric allene (vide infra) and cannot be applied for the generation of a persistent propargyl anion 4.
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24. Hunter, A. D.; Mozol, V.; Tsai, S. D. Organometallics 1992, 11, 2251.
25. 13C NMR and MNDO study on related propargyl anions see, for example: Dem'yanov, P. I.; Styrkov, I. M.; Krut'ko, D. P.; Vener, M. V.; Petrosyan, V. S. J. Organomet. Chem. 1992, 438, 265.
26. Electrophilic trapping reactions with 4: To a cooled solution (-25 to -10 °C) of 105 mg (0.24 mmol) of 3 in 6 mL of THF was added a solution of 0.28 g (1.7 mmol) of LiHDMS in 3 mL of THF. This intense orange-red solution was stirred for 10-15 min at -25 to -10 °C. After an excess of the trapping electrophile (2.5 mmol) had been added neat to the reaction mixture a color change from red to orange was observed. After stirring at that temperature for 10-15 min 10-20 mL of water was added and the cooling was removed. After extraction with dichloromethane and removal of the solvents the residues crystallized from diethyl ether to give the alkyne 5 and the allene 6, respectively; as yellow solids.
27. 4 (448.44): C, 69.64; H, 4.50. Found: C, 69.13; H, 4.51.
28. Deprotonation with n-butyllithium between -52 and -40 °C and subsequent trapping with methyl iodide furnished the expected alkyne 5 in only 20% yield.
29. 4Si (506.59): C, 66.39; H, 5.17. Found: C, 66.27; H, 5.33.
30. 4 (434.41): C, 69.12; H, 4.18. Found: C, 69.35; H, 4.35.