Addition of cycloheptatrienylidene to cis- and trans-1,3-pentadiene and to styrene.  Rearrangement of spiro[2.6]nona-4,6,8-trienes

Waali, Edward E.; Jones, W. M.

doi:10.1021/ja00805a027

Cited by 27 publications

(2 citation statements)

References 6 publications

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“…[50a,63] Less clear-cut, however, is the origin of spirocyclopropane 56, the styrene trapping product. [64,65] Formally, 56 could be formed through a carbene cyclopropanation or an allowed [π2s ϩ π8s] cycloaddition. [66] The lack of optical activity of 56 when optically active cycloheptatetraene is trapped with styrene supports the carbene cyclopropanation route, although Jones et al admitted that this evidence is weak.…”

Section: Inner-phase Chemistrymentioning

confidence: 99%

Inner-Phase Stabilization of Reactive Intermediates

Warmuth

2001

Eur. J. Org. Chem.

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Molecular container compounds are spherical, hollow molecules with inner cavities (inner phases) that are large enough to accommodate a single guest molecule. These inner phases are superb environments for the stabilization and spectroscopic investigation of important reactive intermediates. The surrounding host protects the incarcerated reactive intermediate from dimerization or from a reaction with bulk‐phase reactants that are too large to enter the inner phase by passing through a portal in the host shell.

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Section: Inner-phase Chemistrymentioning

confidence: 99%

Inner-Phase Stabilization of Reactive Intermediates

Warmuth

2001

Eur. J. Org. Chem.

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“…Caled for C,8H,804: C, 72.50; , 6.04. Found: C, 72.79; H, (20) . The same procedure for the preparation of l-phenyl-(6,l 1methano)spiro[2.10]tetradeca-4,6,8,10,12-pentaene (17) was used except that 0.610 g of cyclononadiene was used as the trap instead of styrene.…”

Section: Methodsmentioning

confidence: 99%

Generation and properties of 4,9- and 3,8-methano[11]annulenylidenes

Jones¹,

Labar²,

Brinker³

et al. 1977

J. Am. Chem. Soc.

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Simmons‐Smith Cyclopropanation Reaction

2001

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Almost 30 years after Emschwiller prepared IZnCH 2 I, Simmons and Smith discovered that the reagent formed by mixing a zinc‐copper couple with CH 2 I 2 in ether could be used for the stereospecific conversion of alkenes to cyclopropanes. Nowadays, the Simmons‐Smith cyclopropanation reaction is one of the most widely used reactions in the organic chemist's arsenal for the conversion of olefins into cyclopropanes. This popularity is mainly due to the stereospecificity of the reaction with respect to the double bond geometry and its compatibility with a wide range of functional groups. The chemoselectivity of the reaction toward some olefins is excellent and very few side reactions are observed with functionalized substrates. The metal carbenoid is electrophilic in nature and electron‐rich alkenes usually react much faster than electron‐poor alkenes. Furthermore, the ability to use proximal hydroxy or ether groups to dictate the stereochemical outcome of the CC bond forming process was recognized early on, and this unique property has been successfully exploited on numerous occasions. It has been recognized that halomethylmetal reagents are powerful synthetic tools for the stereoselective addition of a methylene unit to chiral acyclic allylic alcohols and allylic ethers. In addition, the use of halomethylzinc reagents in the presence of chiral additives is one of the few ways to cyclopropanate allylic alcohols efficiently and with good enantiocontrol. Carbenoids can be divided into the following two classes: (1) those of general structure MCH 2 X and (2) those corresponding to M = CH 2 . This chapter is focussed exclusively on the first class in which M = Zn, Sm, or Al. Although other metal carbenoids of type MCH 2 X, such as those derived from Cu, Cd, Hg, and In, have been reported to be effective reagents for the cyclopropanation of some olefins, they have been used only sporadically, and this review does not highlight these reactions. This chapter covers cyclopropanation reactions involving haloalkylzinc, aluminum, and samarium reagents published since the comprehensive chapter in Organic Reactions by Simmons that surveyed the literature up to 1973.

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Addition of cycloheptatrienylidene to cis- and trans-1,3-pentadiene and to styrene. Rearrangement of spiro[2.6]nona-4,6,8-trienes

Cited by 27 publications

References 6 publications

Inner-Phase Stabilization of Reactive Intermediates

Inner-Phase Stabilization of Reactive Intermediates

Generation and properties of 4,9- and 3,8-methano[11]annulenylidenes

Simmons‐Smith Cyclopropanation Reaction

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