Multifurcated halogen bonding involving Ph–Cl⋯H–CPhN–R′ interactions and its relation to idioteloamphiphile layer architecture

Glaser, Rainer; Murphy, Richard F.; Sui, Yongqiang; Barnes, Charles L.; Kim, Sung Hoon

doi:10.1039/b601467d

Cited by 17 publications

(16 citation statements)

References 27 publications

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“…In this case, halogen bonding is usually monitored in terms of shortness of the contacts between halogen atoms and the nucleophile and their angles of approach. In the halogen bonds studied here, the nucleophile is mostly halogen, in other words, we are referring to contacts of the type X + Á Á ÁX À , although it should be noted that it is only the electrophilic halogen X + that renders the name 'halogen bond' possible (Glaser et al, 2006;Metrangolo et al, 2006). This invokes two possibilities for the formation of halogen bonds.…”

Section: Introductionmentioning

confidence: 99%

Halogen bonds in some dihalogenated phenols: applications to crystal engineering

Mukherjee

Desiraju

2013

IUCrJ

189

234

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Section: Introductionmentioning

confidence: 99%

Halogen bonds in some dihalogenated phenols: applications to crystal engineering

Mukherjee

Desiraju

2013

IUCrJ

189

234

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“…We speculate that a redox-mediated donor-acceptor bifunctional mechanism is operating [7,11] and that the chloro group is playing a key role in stabilizing a favorable transition state probably through a decrease in the LUMO level-thus facilitating a possible ratedetermining Ru IV /Ru II step [11a] -and also through a CpH/Cl hydrogen bond. [12] Elucidation of the detailed mechanism is now an on-going project in our research group. Table 1: Enantioselective intramolecular dehydrative cyclization of (E)hept-2-ene-1,7-diol ((E)-1 a) to 2-vinyltetrahydro-2H-pyran (2 a) using a catalytic system consisting of R-naph-pyCOOH 4 or its allyl ester 5 and [CpRu(CH 3 CN) 3 ]PF 6 (3).…”

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confidence: 99%

Asymmetric Dehydrative Cyclization of ω‐Hydroxy Allyl Alcohols Catalyzed by Ruthenium Complexes

2009

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Chiral cyclic ethers constitute one of the most important structural units in biologically active compounds such as polycyclic ethers, polyether antibiotics, acetogenins, as well as coumaran-and chromane-related natural products.[1] Among many key building blocks reported so far, a-alkenyl-substituted cyclic ethers are widely recognized as the most useful because the alkenyl moiety can be transformed into a wide range of functionalities, thereby facilitating further elongation. The development of an efficient strategy for the construction of these cyclic ethers has attracted a great deal of attention over the last two decades. In particular, the focal point is the creation of catalytic enantioselective protocols, which have been categorized into three types: 1) Wacker-type oxidative cyclization of ortho-allyl-or homoallylphenol derivatives, [2] 2) Tsuji-Trost-type intramolecular allylation using w-hydroxy allyl esters, [1c,f, 3] and 3) hydroalkoxylation of alkynes [4] and allenes.[5] Herein, we report a new type of protocol, in which non-activated or non-protected diols 1 dehydratively cyclize into the corresponding cyclic ethers 2 with high regio-and enantioselectivity.We have developed a new chiral ligand-R-naphpyCOOH 4 [naph = naphthyl, py = pyridine, R = substituent (see structures)]-based on the knowledge that a catalytic system combining [CpRu(CH 3 CN) 3 ]PF 6 (3; Cp = cyclopentadienyl) [6] with a pyridine-2-carboxylic acid derivative or the corresponding cationic CpRu IV -p-allyl carboxylato complex can convert a 1:1 mixture of alcohols or allyl alcohols into allyl ethers with the liberation of water.[7] The ligand is characterized by the sterically flexible axial chirality through the C6-C1' bond [8] and the adjustability of electronic and steric properties of the naphthalene ring by changing the R substituent at C2'. The allyl esters R-naph-pyCOOallyl (allyl = CH 2 CH = CH 2 ) 5 were also target ligands because of the convenient formation of the CpRu IV -p-allyl complex directly from 3. A series of compounds 5 a-c were prepared in 44-64 % yield from 2-bromo-3-methylpyridine through a Suzuki-Miyaura coupling between pyridine and naphthalene moieties, modified Reissert-Henze reaction, hydrolysis, and an allyl esterification sequence in combination with MuraiChatani silylation of aromatic C À H bonds and chlorination or phenylation at C2'.[9] The enantiomers were separated by HPLC on a chiral stationary phase, and the absolute configurations were determined by single-crystal X-ray analysis of the ester of (1R,2S,5R)-menthol or the amide of (R)-1-phenylethylamine.[9]The effectiveness of R-naph-pyCOOH 4 and the allyl ester 5 in combination with 3 in the asymmetric dehydrative cyclization was investigated by use of 1 a (C

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“…Only the major component of the disorder is used in the ®gure. The compound is isostructural with (Cl//Cl) (Zheng et al, 2005;Glaser et al, 2006;Ojala et al, 2007). This packing arrangement has no short CNÁ Á ÁCN, CNÁ Á ÁCl or ClÁ Á ÁCl contacts except those arising from the a-axis distance of 3.828 A Ê .…”

Section: Commentmentioning

confidence: 99%

4-(4-Chlorobenzylidenehydrazonomethyl)benzonitrile and the bromo and iodo analogs

Ojala¹,

Ojala²,

Britton³

2008

Acta Crystallogr C

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4-Cyano-4'-chlorobenzalazine [systematic name: 4-(4-chlorobenzylidenehydrazonomethyl)benzonitrile], C(15)H(10)ClN(3), occurs in two polymorphs. Polymorph A is isostructural with the corresponding dichloro compound. Polymorph B is isostructural with the bromo and iodo analogs, viz. C(15)H(10)BrN(3) and C(15)H(10)IN(3), respectively. The latter three structures all have approximately linear C-N...X-C intermolecular contacts in which the N...X contact distances are longer than those in the corresponding benzylideneanilines.

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Multifurcated halogen bonding involving Ph–Cl⋯H–CPhN–R′ interactions and its relation to idioteloamphiphile layer architecture

Cited by 17 publications

References 27 publications

Halogen bonds in some dihalogenated phenols: applications to crystal engineering

Halogen bonds in some dihalogenated phenols: applications to crystal engineering

Asymmetric Dehydrative Cyclization of ω‐Hydroxy Allyl Alcohols Catalyzed by Ruthenium Complexes

4-(4-Chlorobenzylidenehydrazonomethyl)benzonitrile and the bromo and iodo analogs

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