Unusual reagent control of diastereoselectivity in the 1,2-addition of hard carbon nucleophiles to C6-heteroatom substituted cyclohexenones

Organic Letters

Volumn 3, Issue 25, 2001, Pages 4007-4010

  Lindsay, Harriet A ^a   Salisbury, Catherine L ^a   Cordes, Wally ^a   McIntosh, Matthias C ^a  

^a UNIVERSITY OF ARKANSAS   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTINEOPLASTIC AGENT; BREVIONE A; CYCLOHEXANONE DERIVATIVE; HYDROCARBON; INDOLE DERIVATIVE; LITHIUM; MAGNESIUM DERIVATIVE; MANZAMINE A; PYRROLE DERIVATIVE; SPIRO COMPOUND;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; STEREOISOMERISM;

ANTINEOPLASTIC AGENTS, PHYTOGENIC; CYCLOHEXANONES; HYDROCARBONS, CYCLIC; INDOLES; LITHIUM; MAGNESIUM COMPOUNDS; MOLECULAR CONFORMATION; MOLECULAR STRUCTURE; PYRROLES; SPIRO COMPOUNDS; STEREOISOMERISM; SUPPORT, NON-U.S. GOV'T; SUPPORT, U.S. GOV'T, P.H.S.;

EID: 0035856889     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016673j     Document Type: Article

References (74)

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56. nBuLi addition to 3a was performed at room temperature, and the reaction mixture was quenched with HOAc after 5 min. In the absence of an HOAc quench, selective decomposition of the minor product 6b occurred upon prolonged (ca. 90 min) stirring of the reaction mixture at room temperature. Presumably the minor isomer 6b, in which the alkoxide is trans to the chloride, decomposed via formation of the corresponding epoxide. In this case, an apparent selectivity of > 1:20 was observed. See Supporting Information for details.
57. X-ray crystallographic analysis ot alcohol 7c confirmed stereochemical assignments. See Supporting Information for details.
58. Kinetic epimerization of trans-6-chlorocarvone 3a was achieved by adding 3a to a solution of LDA at -78°C followed by addition of a THF solution of camphor sulfonic acid. A 3:1 ratio of 8:3a was obtained with cis-o-chlorocarvone 8 isolated in 64% yield.
59. X-ray crystallographic analysis of an (S)-O-benzyl lactate ester derived from 9 confirmed stereochemical assignments. See Supporting Information for details.
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71. (c) Shi, Z.; Boyd, R. J. J. Am. Chem. Soc. 1993, 115, 9614-9619. Other theoretical studies have investigated selectivity in additions involving Grignard, organolithium, organoaluminum and/or organopotassium reagents: Yadav, V. K.; Sriramurthy, V. Tetrahedron 2001, 57, 3987-3995. See also refs 5c-d.
72. A further complicating factor is the aggregation state of the nucleophile. A number of studies indicate that the molecular aggregation of organolithium and Grignard reagents is dependent upon solvent and the R group and that aggregation affects the reactivity of the nucleophile as well as the mechanism and the stereoselectivity of the addition. (a) Thompson. A.; Corley, E. G.; Huntington, M. F.; Grabowski, E. J. J.; Remenar, J. F.; Collum, D. B. J. Am. Chem. Soc. 1998, 120, 2028-2038.
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