Addition of isopropyllithium in diethyl ether to .alpha.-substituted styrenes.  Quantitative evidence on the stability of cyclopropylcarbinyllithium species

Landgrebe, John A.; Shoemaker, John D.

doi:10.1021/ja00993a039

Cited by 22 publications

(17 citation statements)

References 19 publications

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“…(15), 117 (26), 105 (29), 91 (100), 77 (10). (25), 121 (100), 105 (7), 91 (50), 77 (10), 57 (22). (12), 175 (19), 165 (12), 148 (16), 135 (50), 121 (100), 107 (16), 91 (36).…”

Section: -Phenylheptanoic Acid (3b)unclassified

“…The anionic polymerisation of styrene using organolithium reagents is a well-known process 3 and, presumably for this reason, there are few reports 1,4,5 in the literature of its organometallic addition reactions, although some of its alkenylsubstituted derivatives have been more thoroughly studied. 1,[6][7][8] We recently discovered that organolithium addition reactions to styrene are synthetically viable under appropriate conditions. 9 We went on to develop an enantioselective variant of this process 10 and extended the basic methodology to tetralin synthesis.…”

Section: Introductionmentioning

confidence: 99%

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Organolithium addition to styrene and styrene derivatives: scope and limitations

Wei

Johnson

Taylor

2000

J. Chem. Soc., Perkin Trans. 1

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Styrene and a range of aryl-substituted styrene derivatives are shown to undergo efficient carbolithiation-trapping reactions in diethyl ether at Ϫ78 to Ϫ25 ЊC. The reactivities of different types of organolithium reagents were found to be: tertiary, secondary > primary; ӷ alkenyl, methyl, phenyl. Electron donating groups (e.g. methoxy and dialkylamino) at the ortho-or para-positions of the benzene ring deactivate the double bond towards organolithium addition, but their reactions with butyllithium can be facilitated by using TMEDA as co-solvent. 2-Benzyloxystyrene and 2-allyloxystyrene undergo efficient carbolithiation at Ϫ78 ЊC, but at room temperature alkyl transfer occurs, generating the corresponding alkylated phenol. 2-Vinylnaphthalene also undergoes carbolithiation-carboxylation in reasonable yield.

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“…(15), 117 (26), 105 (29), 91 (100), 77 (10). (25), 121 (100), 105 (7), 91 (50), 77 (10), 57 (22). (12), 175 (19), 165 (12), 148 (16), 135 (50), 121 (100), 107 (16), 91 (36).…”

Section: -Phenylheptanoic Acid (3b)unclassified

Section: Introductionmentioning

confidence: 99%

Organolithium addition to styrene and styrene derivatives: scope and limitations

Wei

Johnson

Taylor

2000

J. Chem. Soc., Perkin Trans. 1

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“…If k > k-1, cyclopropylmethyl compounds of structure (42) accumulate in the reacting system. If k < k-1, the ally1 compounds (44) and (46) are formed by way of the carbonium ions (43) and (45). The preponderance of the trans isomer (44) in the rearrangement products can be best explained by the relative abundance of the low energy conformer (43).…”

Section: ) Imentioning

confidence: 99%

“…If k < k-1, the ally1 compounds (44) and (46) are formed by way of the carbonium ions (43) and (45). The preponderance of the trans isomer (44) in the rearrangement products can be best explained by the relative abundance of the low energy conformer (43). In this connection, the rearrangement of arylcyclopropylmethyloxyborane (47) and of bis(cyclopropy1benzoxy)borane (49) may be considered.…”

Section: ) Imentioning

confidence: 99%

“…The rearranged product from the acid and the phosphorus halide treatment of secondary cyclopropyl alcohol (39), as well as the formation of compounds (44) and (46) from the deamination of dicyclopropylmethylamine (40), R = cyclopropyl, can be explained in terms of initial formation of several isomeric carbonium-ion intermediates (41), (43), and (45).…”

Section: Introductionmentioning

confidence: 99%

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Recent Developments in the Stereochemistry of Cyclopropane Ring Opening

Sarel

Yovell

Sarel-Imber

1968

Angew. Chem. Int. Ed. Engl.

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6-Methylspiro[2.5]octan-4-one (62) is obtained by a similar synthesis from (+)-3-methylcyclohexanone ( 6 1 ) [ 3 4 1 . Compound (62) is the first cyclopropyl ketone whose absolute configuration has been determined. Its Cotton effect does not correspond to the predictions of the octant rule.No ring expansion takes place on dehalogenation of 2,2-bis(bromomethyl)cyclohexanone with zinc; the spiro ketone is formed quantitatively in aqueous methanol after a normal ring closure. The higher cycloalkanone derivatives exhibit both reactions. 2,2-Bis(bromomethy1)cyclooctanone (63) is particularly interesting in this respect, since it can be reduced to the ring expansion product (64) in acetic anhydride/ ether, to a mixture of (64) and the normal ring closure product (65) in aqueous methanol, or exclusively to the ketone (65) in aqueous methanol in the presence of ethylenediaminetetraacetic acid. This review article deals with the stereochemistry of the following ring opening reactions: I . Homoallylic rearrangement of secondary and tertiary cyclopropyl alcohols in the presence of electrophilic reagents, 2. The addition of carboxylic acids to vinylcyclopropanes, 3. The thermal rearrangement of vinylcyclopropanes into cyclopentenes. An account is also given of the N M R spectroscopic determination of the conformations of substituted vinylcyclopropanes.

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Preparation of Ketones from the Reaction of Organolithium Reagents with Carboxylic Acids

Jorgenson

2011

Organic Reactions

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The reaction of organolithium reagents and carboxylic acids constitutes a simple general method for the synthesis of ketones. This preparative route is the method of choice for direct conversion of carboxylic acid to ketones. It is the purpose of this chapter to evaluate critically the scope and limitations of this reaction and to recommend optimal conditions for its applications. The reaction of organolithium reagents with carboxylic acid is limited to the preparation of acyclic ketones. Although the objective of this reaction, the formation of unsymmetrical ketones, the method is clearly applicable to the synthesis of symmetrical ketones. Two different routes are possible and are discussed. To date, the reaction has been applied only to the preparation of monoketones.

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Addition of isopropyllithium in diethyl ether to .alpha.-substituted styrenes. Quantitative evidence on the stability of cyclopropylcarbinyllithium species

Cited by 22 publications

References 19 publications

Organolithium addition to styrene and styrene derivatives: scope and limitations

Organolithium addition to styrene and styrene derivatives: scope and limitations

Recent Developments in the Stereochemistry of Cyclopropane Ring Opening

Preparation of Ketones from the Reaction of Organolithium Reagents with Carboxylic Acids

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