Reactive Intermediates in the Bicyclo[3.1.0]hexyl and Bicyclo[3.1.0]hexylidene Systems. I. The Acid-Catalyzed Addition of Methanol and Acetic Acid to Bicyclo[3.1.0]hexene-2<sup>1</sup>

Freeman, Peter K.; Grostic, Marvin F.; Raymond, Floyd A.

doi:10.1021/jo01014a029

Cited by 42 publications

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“…23 The similar role of the bent bond was observed in electrophilic additions to bicyclo[3.1.0]hexene (eq 4). 24 The stereochemistry of the methanolysis products from 4-bicyclo[3.1.0]hexenyl trifluoroacetate X (eq 5)25 is also explained by the nonequivalent LUMO extension of the allyl moiety. Syn-anti isomerism in the Diels-Alder reaction (eq 6) can also be discussed in terms of nonequivalent extension of a frontier orbital.…”

Section: Application and Discussionmentioning

confidence: 99%

“…Actually the effect due to such small difference in position is completely negligible for the present discussion: in fact at the P point, V is equal to 9.7 kcal/mol. (24) For instance a rationalization of the mutual polarization effects could be obtained by means of a geminal description of the interacting groups. (25) Differential electrostatic polarization can be usefully introduced, for example, in the interpretation of NMR spectra.…”

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confidence: 99%

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Orbital mixing rule

Inagaki¹,

Fujimoto²,

Fukui³

1976

J. Am. Chem. Soc.

251

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Section: Application and Discussionmentioning

confidence: 99%

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confidence: 99%

Orbital mixing rule

Inagaki¹,

Fujimoto²,

Fukui³

1976

J. Am. Chem. Soc.

251

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“… a Isolated yield of diiodide from corresponding primary iodide. b Isolated yield of bicyclohexane. c OTHP group used as directing group due to volatility of the low-molecular weight MOM-protected products. d By 1 H NMR (ref ). …”

Section: Resultsmentioning

confidence: 99%

Intramolecular Simmons−Smith Cyclopropanation. Studies into the Reactivity of Alkyl-Substituted Zinc Carbenoids, Effect of Directing Groups and Synthesis of Bicyclo[n.1.0]alkanes

Bull

Charette

2010

J. Am. Chem. Soc.

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An intramolecular Simmons-Smith (IMSS) cyclopropanation has been developed, providing a novel method for the construction of substituted bicycloalkanes. First, functionalized gem-diiodoalkanes containing allylic alcohols were prepared in high yield. Then the intramolecular cyclization to form different ring sizes was investigated and proved to be successful for the synthesis of bicyclo[3.1.0]hexanes and bicyclo[4.1.0]heptanes. Larger chain lengths led to terminal alkene-containing products. Analysis of the product distribution for the different ring sizes and under various reaction conditions provided insight into the reactivity of substituted zinc carbenoids, and by the appropriate choice of conditions cyclopropanation could be promoted over alternative reaction pathways. Next the ability of allylic groups to promote the IMSS reaction by directing the zinc carbenoid was examined for the formation of bicycloheptanes. A scale of 'directing-ability' for these allylic groups has been rationalized, with an OMOM directing group providing the greatest enhancement in formation of the bicycle. Finally, the scope of the cyclization in forming substituted bicyclo[3.1.0]hexanes was explored. Substitution on the alkene and at the allylic position was well tolerated, providing the bicyclic products in high yields. Additionally, the IMSS reaction allowed a highly diastereoselective synthesis of a 5-3-5 fused tricycloalkane. These studies will have implications for the use of substituted carbenoids in cyclopropanation reactions and for directed cyclopropanation reactions as well as in the synthesis of substituted bicycloalkanes.

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“…Caled for C25H24N2O: C, 81.52; H, 6.52; N, 7.60. Found: C, 81.63; H, 6.73; N, 7.85. Ethyl N-(l,2,3-Triphenylcycloprop-2-enylcarbinyl)carbamate (11) and 3,4,.-A dry ether solution of 8b (from 0.41 g of acid chloride) was added dropwise to 8 ml of refluxing, stirred, dry benzene over the course of 20 min. After the addition was complete, the benzene-ether solution was refluxed for an additional 25 min.…”

Section: Methodsmentioning

confidence: 99%

Strained organic molecules. II. Rearrangements of 1-(1,2,3-triphenylcycloprop-2-enyl)-3-diazopropan-2-one (1,2,-3-triphenylcycloprop-2-enyl)acetyl azide

Monahan¹,

Tang²

1968

J. Org. Chem.

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Several reactions are discussed. In the presence of silver benzoate, triethylamine, and ethanol, 1-( 1,2,3-triphenylcycloprop-2-enyl)-3-diazopropan-2-one ( 1 b) rearranges to two isomers of ethyl ( 1,2-diphenylcyclobut-2-eny1)phenylacetate (6a and b). Thermally, (1,2,3-triphenylcycloprop-2-enyl)acetyl azide (8b) rearranges to the corresponding isocyanate which was trapped with either dimethylamine or ethanol. With ultraviolet light the azide follows a different pathway.

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Reactive Intermediates in the Bicyclo[3.1.0]hexyl and Bicyclo[3.1.0]hexylidene Systems. I. The Acid-Catalyzed Addition of Methanol and Acetic Acid to Bicyclo[3.1.0]hexene-2¹

Cited by 42 publications

References 0 publications

Orbital mixing rule

Orbital mixing rule

Intramolecular Simmons−Smith Cyclopropanation. Studies into the Reactivity of Alkyl-Substituted Zinc Carbenoids, Effect of Directing Groups and Synthesis of Bicyclo[n.1.0]alkanes

Strained organic molecules. II. Rearrangements of 1-(1,2,3-triphenylcycloprop-2-enyl)-3-diazopropan-2-one (1,2,-3-triphenylcycloprop-2-enyl)acetyl azide

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Reactive Intermediates in the Bicyclo[3.1.0]hexyl and Bicyclo[3.1.0]hexylidene Systems. I. The Acid-Catalyzed Addition of Methanol and Acetic Acid to Bicyclo[3.1.0]hexene-21

Cited by 42 publications

References 0 publications

Orbital mixing rule

Orbital mixing rule

Intramolecular Simmons−Smith Cyclopropanation. Studies into the Reactivity of Alkyl-Substituted Zinc Carbenoids, Effect of Directing Groups and Synthesis of Bicyclo[n.1.0]alkanes

Strained organic molecules. II. Rearrangements of 1-(1,2,3-triphenylcycloprop-2-enyl)-3-diazopropan-2-one (1,2,-3-triphenylcycloprop-2-enyl)acetyl azide

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Reactive Intermediates in the Bicyclo[3.1.0]hexyl and Bicyclo[3.1.0]hexylidene Systems. I. The Acid-Catalyzed Addition of Methanol and Acetic Acid to Bicyclo[3.1.0]hexene-2¹