Carbocyclization Reaction of ω-Iodo- and 1,ω-Diiodo-1-alkynes without the Loss of Iodine Atoms through a Carbenoid-Chain Process

Harada, Toshiro; Muramatsu, Keiko; Mizunashi, Kenta; Kitano, Chie; Imaoka, Daisuke; Fujiwara, Takayuki; Kataoka, Hiroshi

doi:10.1021/jo7021179

Cited by 30 publications

(11 citation statements)

References 53 publications

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“…Two equivalents of 6, prepared via precursor 5 [18] in two steps (see Scheme S1 in the Supporting Information), was heated with 7 [15] and Cs 2 CO 3 in dry DMF to afford the macrocycle precursor 8 in 59 % yield following purification by silica gel chromatography. Macrocyclisation of 8 by Eglinton coupling [19] of the terminal alkyne groups was carried out using copper(II) acetate under high dilution conditions in acetonitrile (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

“…Compounds 2·X, [15,16] 3·X (where X = PF 6 , I, Br, Cl), [4] 5, [18] 7 [15] and 9 [17] were prepared according to literature procedures. The synthesis and characterisation of 6 has been reported previously.…”

Section: Methodsmentioning

confidence: 99%

“…The synthesis and characterisation of 6 has been reported previously. [18] A new preparation of 6 is reported in the Supporting Information.…”

Section: Methodsmentioning

confidence: 99%

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Kinetic Studies Exploring the Role of Anion Templation in the Slippage Formation of Rotaxane‐Like Structures

McConnell

Beer

2011

Chemistry A European J

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The first examples of the slippage formation of rotaxane-like structures in the presence of an anion template are reported between a macrocycle, synthesised by exploiting Eglinton coupling, and stoppered pyridinium axle components. The role of the anion template in the slippage process has been explored by kinetic studies. (1)H NMR spectroscopic investigations reveal the slippage species formed are not rotaxanes but pseudorotaxanes with some rotaxane character. The anion template significantly influences the amount of rotaxane character and the rate of slippage. Importantly, the fastest slippage rates, k(on), are achieved with the non-coordinating hexafluorophosphate anion, whereas the slowest slippage off rates, k(off), are observed in the presence of coordinating anions, such as chloride. Since the k(off) rates are significantly smaller than the k(on) rates in the presence of coordinating anions, these anions act as templates favouring formation of the slippage species thermodynamically. Consequently, the resulting pseudorotaxanes with coordinating anions have greater rotaxane character. Two strategies for converting the slippage pseudorotaxanes into rotaxanes using hydrogenation or complexation with cobalt carbonyl are investigated.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

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Kinetic Studies Exploring the Role of Anion Templation in the Slippage Formation of Rotaxane‐Like Structures

McConnell

Beer

2011

Chemistry A European J

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“…(α ‐ICyD )CuCl was synthesized according to our previously published procedure. [1a] Alkynes 1o , 4b , and 4c , were prepared according to reported procedures.…”

Section: Methodsmentioning

confidence: 99%

Carboboration of Alkynes with Cyclodextrin‐Encapsulated N‐Heterocyclic Carbene Copper Complexes

et al. 2019

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The copper‐catalyzed carboboration of various alkynes was investigated with a modified N‐heterocyclic carbene‐capped α‐cyclodextrin copper(I) complex in which the reactive copper center is deeply encapsulated in the cyclodextrin (CD) cavity. The methylborylation of terminal alkynes was found to give linear (L) (E)‐vinyl boron isomers as the major isomers, as expected from the previously proposed “perpendicular” approach of the alkyne to the Cu–B bond, and methylation of the vinyl boron copper intermediate. Under similar conditions, the intramolecular carboboration reaction with terminal alkynes functionalized by alkyl halides, led to exocyclic vinyl boronate species as the major isomer. However, an endocyclic (Z)‐isomer was also observed in some cases. This isomer was not previously observed and is unexpected considering the “classical” mechanism. The direct generation of boron functionalized (Z)‐alkenes by carboboration of alkynes is unprecedented.

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“…Compounds 5c,d have not been previously reported, while 5b was recently obtained by another procedure (using -OTs for Iexchange). 28…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Podands with Cyanurate or Isocyanurate Cores and Terminal Triple Bonds

Piron¹,

Oprea²,

Cismas³

et al. 2010

Synthesis

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P o d a n d s w i t h C y a n u r a t e a n d I s o c y a n u r a t e C o r e s Abstract: The synthesis of podands with cyanuric or isocyanuric acid cores and oligoethyleneoxy pendant arms exhibiting terminal triple bonds or brominated triple bonds is reported. The starting material for cyanuric acid derived podands is commercially available cyanuric acid, while the isocyanuric derivatives are obtained by thermal isomerization of the corresponding cyanurates.

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Carbocyclization Reaction of ω-Iodo- and 1,ω-Diiodo-1-alkynes without the Loss of Iodine Atoms through a Carbenoid-Chain Process

Cited by 30 publications

References 53 publications

Kinetic Studies Exploring the Role of Anion Templation in the Slippage Formation of Rotaxane‐Like Structures

Kinetic Studies Exploring the Role of Anion Templation in the Slippage Formation of Rotaxane‐Like Structures

Carboboration of Alkynes with Cyclodextrin‐Encapsulated N‐Heterocyclic Carbene Copper Complexes

Synthesis of Podands with Cyanurate or Isocyanurate Cores and Terminal Triple Bonds

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