Reaction of 1,2-Dehydro-o-carborane with Acetylenes. Synthesis and Structure of a Carborane Analog of Benzocyclobutadiene

Ho, Douglas M.; Cunningham, Robert J.; Brewer, Judson A.; Bian, Nanying; Jones, Maitland

doi:10.1021/ic00125a028

Cited by 58 publications

(11 citation statements)

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“…The chemistry of o -carborane ( 1 ) has several parallels with benzene. − Jones and co-workers have brought out yet another amazing parallel between these two prototypes: the 1,2-dehydro- o -carborane ( 2 ) is shown to be comparable in reactivity to 1,2-dehydrobenzene (benzyne) ( 3 ). Derivatives of disila-analogs should provide equally interesting chemistry.…”

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confidence: 99%

Structure and Bonding in B₁₀X₂H₁₀ (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

Jemmis

Kiran

1997

J. Am. Chem. Soc.

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The chemistry of o-carborane (1) has several parallels with benzene. [1][2][3] Jones and co-workers 4 have brought out yet another amazing parallel between these two prototypes: the 1,2-dehydroo-carborane (2) is shown to be comparable in reactivity to 1,2dehydrobenzene (benzyne) (3). Derivatives of disila-analogs should provide equally interesting chemistry. Seyferth and coworkers 5 have synthesized a dimethyl derivative of 4. Despite the structural similarity between 1 and 4, they differ substantially in their reactivity patterns. Nucleophilic bases attack the dimethyl derivative of 4 resulting in the loss of an MeSi vertex; whereas, in 1 the reaction is centered on a boron adjacent to the carbon. 6 Will the behavior of B 10 Si 2 H 10 follow that of the carbon analog? The structure of Si 2 H 4 contrast dramatically with that of ethylene. 7,8 Constraints of an icosahedral skeleton make any guess on the structure of the B 10 Si 2 H 10 even more hazardous. This paper compares the C-C double bonds in 2 and 3 and unravels an unexpected kinky structure for B 10 Si 2 H 10 .The structures 1-6 and 11 were optimized at the HF/6-31G* and B3LYP/6-31G* levels of theory. 9,10 Total energies and important parameters are given in Table 1. Unless otherwise stated, B3LYP energies and bond parameters are used in the discussion. The structure of o-carborane has been studied by several theoretical methods. 11 The structure is calculated to be

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confidence: 99%

Structure and Bonding in B₁₀X₂H₁₀ (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

Jemmis

Kiran

1997

J. Am. Chem. Soc.

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“…Jones and co-workers have reported the reaction of 1,2-dehydro-o-carborane with acetylenes that produced the carborane analog of benzocyclobutadiene. 121 1,2-Dehydroo-carborane (88) (Fig. 54), which is obtained from o-carborane by treatment with n-BuLi and Br 2 , was found to add 3-hexyne to give the product of an ene reaction and with 1-phenyl-1-propyne (87) to give the products of both an ene reaction (89) and a 2ϩ2 reaction (90) similar to the reactivity of benzene (Fig.…”

Section: Monomeric and Polymeric Organic Analogs Of Boron Cluster Sys...mentioning

confidence: 94%

The State of the Art in Boron Polymer Chemistry

Kolel-Veetil¹,

Keller²

2006

Macromolecules Containing Metal and Metal‐Like Elements

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I. INTRODUCTION A. A Brief Historical Perspective on Boron and Its PolymersBoron (Buraq in Arabic/Burah in Persian, which is the word for "white," the color being attributed to borax (sodium tetraborate, Na 2 B 4 O 7 .10H 2 O)) was discovered in 1808 independently by the British Chemist, Sir Humphry Davy, and two French chemists, Joseph Louis Gay-Lussac and Loius Jacques Thenard. 1 They isolated boron in 50% purity by the reduction of boric acid with sodium or magnesium. The Swedish chemist Jons Jakob Berzilius identified boron as an element in 1824. The first pure sample of boron was produced by the American chemist William Weintraub in 1909. Boron does not appear in nature in elemental form, but is found in its compounded

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“…Like benzyne, 33 o-carboryne reacts with aliphatic internal alkynes such as 3-hexyne to give the product of ene reaction in more than 99% relative yields, whereas it adds in both ene and [2 + 2] fashions to 1-phenyl-1-propyne to yield carboranylallene and cyclobutenocarborane, respectively (Scheme 13). 34,35 On the other hand, strained cycloalkynes effectively interfere with the ene reaction, and only cyclobutenocarboranes are obtained in the reaction with cyclooctyne and 3,3,6,6-tetramethyl-1-thia-4-cycloheptyne (Scheme 13). 12 Terminal alkynes would neutralize the cage C-Li bond of the precursor and therefore they are not suitable substrates.…”

Section: Reaction With Alkynesmentioning

confidence: 99%

Generation and reactivity of o-carborynes

Qiu

Xie

2014

Dalton Trans.

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o-Carboryne (1,2-dehydro-o-carborane) is a very reactive intermediate that can be generated in situ from 1-Br-2-Li-1,2-C2B10H10, 1-I-2-Li-1,2-C2B10H10 or 1-Me3Si-2-[IPh(OAc)]-1,2-C2B10H10. It exists in two resonance forms, a bonding form vs. a biradical form. Each form demonstrates unique reactivity patterns. o-Carboryne can undergo various types of reactions such as [4 + 2]/[2 + 2] cycloaddition, ene reaction, hydrogen abstraction, and sp(2)/sp(3) C-H bond insertion reaction with a broad spectrum of substrates including alkenes, alkynes, (hetero)aromatics, ethers, and ferrocenes. It is a very useful synthon for generating a variety of functionalized carboranes that have potential applications in medicine, materials science and organometallic/coordination chemistry. This perspective offers an overview of recent advances in this interesting research field.

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Reaction of 1,2-Dehydro-o-carborane with Acetylenes. Synthesis and Structure of a Carborane Analog of Benzocyclobutadiene

Cited by 58 publications

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Structure and Bonding in B₁₀X₂H₁₀ (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

Structure and Bonding in B₁₀X₂H₁₀ (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

The State of the Art in Boron Polymer Chemistry

Generation and reactivity of o-carborynes

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Reaction of 1,2-Dehydro-o-carborane with Acetylenes. Synthesis and Structure of a Carborane Analog of Benzocyclobutadiene

Cited by 58 publications

References 0 publications

Structure and Bonding in B10X2H10 (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

Structure and Bonding in B10X2H10 (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

The State of the Art in Boron Polymer Chemistry

Generation and reactivity of o-carborynes

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Structure and Bonding in B₁₀X₂H₁₀ (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane

Structure and Bonding in B₁₀X₂H₁₀ (X = C and Si). The Kinky Surface of 1,2-Dehydro-o-disilaborane