Carbenes from Derivatives of Ethynylcarbinols. The Synthesis of Alkenylidenecyclopropanes<sup>1</sup>

Hartzler, H. D.

doi:10.1021/ja01485a025

Cited by 91 publications

(29 citation statements)

References 2 publications

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“…In 1961, Hartzler investigated the ozonolysis of cyclopropenyl allenes and was possibly the first to propose the occurence of an alkenyl peroxide in solution . Reaction of 42 in ethanol generated α‐hydroxy‐ester 43 , in addition to acetone as the major product (Scheme ).…”

Section: Solution Chemistrymentioning

confidence: 99%

Alkenyl and Aryl Peroxides

Klußmann

2017

Chemistry A European J

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Alkenyl and aryl peroxides are a special class of organic peroxides. Under ambient conditions, they are usually short-lived, rapidly decomposing into radicals by homolytic O-O bond cleavage. They play an important role in the chemistry of the lower atmosphere, where they are formed through ozonolysis of alkenes. In the dark, this pathway is considered the major source of hydroxyl radicals, the "detergent of the atmosphere". In solution, alkenyl and aryl peroxides can be formed by various methods and their decomposition can be harnessed synthetically. For example, reactions involving alkenyl peroxides can be used to introduce ketones through radical additions, and nucleophilic aromatic substitution reactions generating aryl peroxides have been used to synthesize phenols. The radicals can also initiate radical polymerization reactions or chain reactions and mediate oxidative coupling by C-H bond functionalization. Knowledge of their chemistry could be helpful for projects generating or utilizing peroxides.

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Section: Solution Chemistrymentioning

confidence: 99%

Alkenyl and Aryl Peroxides

Klußmann

2017

Chemistry A European J

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“…[21] The synthesis of compound 37 was achieved by addition of propenylidene to 1,1-dimethylindene using the method of Hartzler [22] (Scheme 17). After separation of the exo and endo isomers, the respective enantiomers could be separated by HPLC, using a triacetylcellulose column and providing the isomers in optically pure form.…”

Section: Thermolysis Of 33mentioning

confidence: 99%

“…Ϫ MS (70 eV); m/z (%): 148(14) [M ϩ ], 133 (84), 115(15), 105 (100), 91 (56), 77(28), 65(22), 51(19), 41 (53). 139.3.…”

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confidence: 99%

Trimethylenemethane Derivatives Stabilized by Conjugation II − Concerted or Nonconcerted Generation?

Roth

Wildt

Schlemenat

2001

European J Organic Chem

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The concerted formation of the orthogonal trimethylene-type diradicals 3, 6, and 12 has been demonstrated for the three homofulvenes 2, 4, and 7 and shown to proceed preferentially in a disrotatory manner. The same type of orthogonal diradicals are formed, but in a nonconcerted fashion, from the bicyclic methylenecyclopropanes 26, 30, 33, and 40, through the planar diradicals 28, 31, 35, and 50, respectively.

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“…(Dimethylvinylidene)carbene (1), which was generated easily by the elimination of hydrogen halides from propargyl halides 2 or haloallenes 3 has been used extensively in the stereospecific cyclopropanation of olefins to give the corresponding cyclopropanes (Scheme 1).1, 5 Hartzler has found that a more alkyl substituted olefin possesses greater relative reactivity toward the addition of carbene 1.…”

Section: Introductionmentioning

confidence: 99%

The Regioselectivity of (Dimethylvinylidene)carbene Directed by Aromatic Ring upon the Addition into Aryl Alkenes in the Presence of Other Olefins

Sheu¹,

Yen²,

Huang³

1993

J Chinese Chemical Soc

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Regioselective cycloaddition of (dimethylvinylidene)carbene (1) into aryl alkenes in the presence of other olefins is reported. The reaction is presumably controlled by the phenyl group, which forms an aromatic π‐complex with the carbene C‐3 orbital, followed by the selective addition of 1 to the closest phenyl‐substituted double bond. Also, this selectivity is assumed to be attributed to delocalization of aromatic π electrons which increases the electron density of the conjugated carbon‐carbon double bond, thus leading to the facile addition of vinylidenecarbene.

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Carbenes from Derivatives of Ethynylcarbinols. The Synthesis of Alkenylidenecyclopropanes¹

Cited by 91 publications

References 2 publications

Alkenyl and Aryl Peroxides

Alkenyl and Aryl Peroxides

Trimethylenemethane Derivatives Stabilized by Conjugation II − Concerted or Nonconcerted Generation?

The Regioselectivity of (Dimethylvinylidene)carbene Directed by Aromatic Ring upon the Addition into Aryl Alkenes in the Presence of Other Olefins

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Carbenes from Derivatives of Ethynylcarbinols. The Synthesis of Alkenylidenecyclopropanes1

Cited by 91 publications

References 2 publications

Alkenyl and Aryl Peroxides

Alkenyl and Aryl Peroxides

Trimethylenemethane Derivatives Stabilized by Conjugation II − Concerted or Nonconcerted Generation?

The Regioselectivity of (Dimethylvinylidene)carbene Directed by Aromatic Ring upon the Addition into Aryl Alkenes in the Presence of Other Olefins

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Carbenes from Derivatives of Ethynylcarbinols. The Synthesis of Alkenylidenecyclopropanes¹