Titanocene(II)-promoted reactions of thioacetals with organic molecules having a multiple bond

Reviews on Heteroatom Chemistry

Volumn 21, Issue , 2000, Pages 93-115

  Takeda, Takeshi ^a   Fujiwara, Tooru ^a  

^a TOKYO UNIVERSITY OF AGRICULTURE AND TECHNOLOGY   (Japan)

Author keywords

Carbene complex; Desulfurization; Thioacetal

Indexed keywords

EID: 0033475262     PISSN: 09156151     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article

References (79)

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16. Because water prevents the reduction of 4, dried reagents should be used for the preparation of low-valent titanium 12. In the case of a small-scale experiment (less than 2 mmol), all the solid reagents are placed in a flask and conveniently dried by heating with a heat gun under reduced pressure (2-3 mmHg). During this procedure, care is taken not to sublime 4. If all the reagents are well dried, the reduction of titanocene dichloride is initiated by a change of color (dark green to dark brown) within 15 min after the addition of triethyl phosphite. However, in a large-scale reaction, drying the reagents with a heat gun is not efficient. Therefore, vacuum drying of 4 and inclusion of molecular sieve 4A with stirring at 100°C for 1 h is recommended. The following is a representative method for carbonyl olefination (see Section 3) using a large quantity of 12:a) A 300-ml round-bottomed flask, equipped with a magnetic stirring bar, a thermometer and a rubber septum, is charged with 4 (6.54 g, 26.3 mmol) and finely powdered molecular sieve 4A (1.31 g). The mixture is stirred and warmed in a heating bath at 100°C for l h under reduced pressure (2 mmHg). After cooling, the reaction vessel is flushed with argon and magnesium turnings (0.766 g, 31.5 mmol; purchased from Nacalai Tesque Inc. Kyoto, Japan) are added. THF (42 ml) and triethyl phosphite (8.96 ml, 52.5 mmol) are injected successively through the septum. During the addition of triethyl phosphite, the reaction mixture is cooled in a water bath to maintain the temperature below 30°C. After being stirred for 3 h at room temperature, a THF (14 ml) solution of 1,1-bis(phenylthio)cyclobutane (2.29 g, 8.40 mmol) is injected, and the reaction mixture is stirred for 15 min. Then, a THF solution (21 ml) of S-isopropyl 3-phenylpropanethioate (1.46 g, 7.00 mmol) is injected dropwise over 10 min and the reaction mixture is refluxed for 1 h. After cooling, 1M NaOH (150 ml) is added and the insoluble materials are filtered through celite and washed with ether. The aqueous layer is separated and extracted with ether. The combined extracts are dried with anhydrous sodium sulfate, filtered, and evaporated with a rotary evaporator. The residual liquid is purified by column chromatography (silica gel, hexane) to afford 1.33 g (77%) of (1-isopropylthio-3-phenylpropan-1-ylidene)cyclobutane. a) T. Takeda, Y. Kato and T. Fujiwara: unpublished results.
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