When ethyl is infinitely different from methyl: Double addition of lithiated dithianes to aromatic carboxylates revisited

Journal of Organic Chemistry

Volumn 71, Issue 13, 2006, Pages 5047-5049

  Valiulin, Roman A ^a   Kottani, Rudresha ^a   Kutateladze, Andrei G ^a  

^a UNIVERSITY OF DENVER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DITHIANE RING; ELECTRON-TRANSFER REDUCTION; LITHIATED DITHIANES; METHYL BENZOATE;

ADDITION REACTIONS; ALCOHOLS; ESTERS; NEGATIVE IONS;

AROMATIC HYDROCARBONS;

2 BENZOYLDITHIANE; ACETOPHENONE; ACETOPHENONE DERIVATIVE; ALKANE DERIVATIVE; ALKYL GROUP; AROMATIC COMPOUND; BENZENE DERIVATIVE; BENZENECARBONYL CHLORIDE; BENZOIC ACID DERIVATIVE; BENZYL ALCOHOL DERIVATIVE; CARBOXYLIC ACID DERIVATIVE; DITHIANE; DITHIANYL ION; ESTER; ETHYL GROUP; ION; KETYL ANION RADICAL; LITHIODITHIANE DERIVATIVE; LITHIUM DERIVATIVE; METHYL BENZOATE; METHYL GROUP; RADICAL; THIOL DERIVATIVE; THIOORTHO ESTER; UNCLASSIFIED DRUG;

ADDITION REACTION; ARTICLE; COREY SEEBACH BISADDITION; DOUBLE ADDITION REACTION; ELECTRON TRANSPORT; REDUCTION; RING OPENING;

CARBOXYLIC ACIDS; HYDROCARBONS, AROMATIC; LITHIUM; MOLECULAR STRUCTURE; QUINOLIZINES; SULFHYDRYL COMPOUNDS; SULFUR COMPOUNDS;

EID: 33745468873     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo060780f     Document Type: Article

References (12)

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2. (b) Corey, E. J.; Seebach, D. Angew. Chem., Int. Ed. Engl. 1965, 4, 1077.
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5. (e) Groebel, B. T.; Seebach, D. Synthesis 1977, 357.
6. See ref 1d, although examples of high-yielding double addition of unsubstituted lithiodithiane to benzoyl chloride are known: Kita, Y.; Sekihachi, J.-I.; Hayashi, Y.; Da, Y.-Z.; Yamamoto, M.; Akai, S. J. Org. Chem. 1990, 55, 1108.
7. Li, Z.; Kutateladze, A. G. J. Org. Chem. 2003, 68 (21), 8236.
8. We found that at room temperature addition of butyllithium to a THF solution of dithiane generates >90% anion within 15-20 min after which it slowly degrades. Most of the reactions with carbonyl compounds occur at room temperature at much higher rates, within minutes furnishing the desired adducts in excellent yields, even in the case of less-reactive aromatic ketones, for which the reaction time at low temperatures can be as long as 12-24 h (ref 1d).
9. Gustafson, T. P.; Kurchan, A. N.; Kutateladze, A. G. Tetrahedron 2006, 62.
10. Bulman Page, P. C.; Wilkes, R. D.; Namwindwa, E. S.; Witty, M. J. Tetrahedron 1996, 52, 2125.
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12. Photochemistry of tagged compounds will be described in detail elsewhere.