Catalytic and Highly Efficient 1,4-Addition of Terminal Alkynes to Conjugated Enones by [RuCl2(p-cymene)]2/Pyrrolidine

Organic Letters

Volumn 3, Issue 13, 2001, Pages 2089-2091

  Chang, Sukbok ^a   Na, Youngim ^a   Choi, Eunjung ^a   Kim, Sunggak ^b  

^a Ewha Womans University   (South Korea)

^b Korea Advanced Institute of Science and Technology (KAIST)   (South Korea)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000793297     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016047m     Document Type: Article

References (36)

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15. Although this conversion has been previously accomplished in several ways based upon Al, B, and Sn chemistry, all of these methods require the use of stoichiometric amounts of some metal species, see: (a) Schwartz, J.; Carr, D. B.; Hansen, R. T.; Dayrit, F. M. J. Org. Chem. 1980, 45, 3053.
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23. 2 (2 mol %)/pyrrolidine (0.1 equiv) under otherwise identical conditions afforded a 55% GC yield compared to entry 5 in Table 1.
24. +] 208.1828, found 208.1825.
25. Substituted enones were poorer Michael acceptors compared to ethenyl ketones. For example, reaction of 1-decyne and cyclohexenone afforded a 20-25% yield of the desired product under the same reaction conditions and the starting materials were recovered unchanged.
26. When 1-decyne was reacted with 2.0 equiv of MVK under otherwise identical conditions, the desired product was isolated in 75% yield compared to entry 1 of Table 2. Due to the fact that reaction rates were very similar regardless of the types of the employed enons, high volatility of MVK or ethyl vinyl ketone is regarded as one of the main reasons for requiring large excess amounts of those enones (3.0 equiv) to alkynes for good yields.
27. 2 with 3-hydroxy-2-pyridone in the presence of a base, see: Piotrowski, H.; Polborn, K.; Hilt, G.; Severin, K. J. Am. Chem. Soc. 2001, 123, 2699.
28. 1H NMR spectra are formed in which the integral ratio of p-cymene vs pyrrolidine is 1:1. The chemical shifts of p-cymene peaks in the amine-coordinated complex are changed as well as the coupling constants: see the Supporting Information.
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