- Molecular Chirality and Cloud Activation Potentials of Dimeric α-Pinene Oxidation Products
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The surface activity of ten atmospherically relevant α-pinene-derived dimers having varying terminal functional groups and backbone stereochemistry is reported. We find ~10% differences in surface activity between diastereomers of the same dimer, demonstrating that surface activity depends upon backbone stereochemistry. Octanol-water (KOW) and octanol-ammonium sulfate partitioning coefficient (KOAS) measurements of our standards align well with the surface activity measurements, with the more surface-active dimers exhibiting increased hydrophobicity. Our findings establish a link between molecular chirality and cloud activation potential of secondary organic aerosol particles. Given the diurnal variations in enantiomeric excess of biogenic emissions, possible contributions of such a link to biosphere:atmosphere feedbacks as well as aerosol particle viscosity and phase separation are discussed.
- Bé, Ariana Gray,Bellcross, Aleia,Geiger, Franz M.,Thomson, Regan J.
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p. 16653 - 16662
(2021/10/20)
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- Transformations of Peroxide Ozonolysis Products of (–)-α-Pinene and (+)-3-Carene by the Action of 4-Hydroxybenzohydrazide
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Abstract: Treatment of peroxide ozonolysis products of the bicyclic monoterpenes (–)-α-pinene and (+)-3-carene with 4-hydroxybenzohydrazide in methylene chloride or tetrahydrofuran gave the corresponding keto acids, whereas keto esters were formed in methanol.
- Garifullina, L. R.,Ishmuratov, G. Yu.,Myasoedova, Yu. V.,Nurieva, E. R.
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p. 1673 - 1676
(2020/10/22)
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- Synthesis of Isonicotinic and Salicylic Acids Derivatives from (–)-α-Pinene and (+)-Δ3-Carene
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Abstract: Optically active cyclobutanediyl- and cyclopropanediylbisalkylidenedihydrazides of isonicotinic and salicylic acids were synthesized when theperoxide products of ozonolysis of (–)-α-pinene and(+)-Δ3-carene were reduced with isonicotin
- Garifullina, L. R.,Ishmuratov, G. Yu.,Myasoedova, Yu. V.,Nurieva, E. R.
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p. 2038 - 2042
(2020/12/23)
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- Synthesis of optically active macrolides bearing di- and triethylene glycol and dicarboxylic acid hydrazide moieties from (-)-α-pinene
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Six optically active macroheterocycles bearing ester and dihydrazide moieties were synthesized from available natural (-)-α-pinene through the intermediate keto acid, (31R,33R)- 1-hydroxy-32,32-dimethyl-1,4-dioxopentaphane, using the [2+1] reaction of this keto acid with di- or triethylene glycols and the [1+1] condensation of the resulting α,ω-diketo diesters with dicarboxylic acid dihydrazides in the key steps.
- Yakovleva,Mingaleeva,Denisova,Ishmuratov, G. Yu.
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p. 1445 - 1450
(2019/08/12)
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- Transformations of (-)-α-pinene peroxide ozonolysis products by hydrazines of HCL and H2SO4
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The reactivities of hydrazines of HCl and H2SO4 for (-)-α-pinene peroxide ozonolysis products were studied. It was shown that these reagents were less effective and selective than semicarbazide hydrochloride for transformations into cis-pinonic acid and its esters.
- Legostaeva, Yu. V.,Garifullina,Nazarov,Kravchenko,Ishmuratov, G. Yu.
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p. 1020 - 1022
(2018/03/21)
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- Transformations of peroxide products of olefin ozonolysis in tetrahydrofuran in reactions with hydroxylamine and semicarbazide hydrochlorides
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Treatment with hydroxylamine and semicarbazide hydrochlorides of peroxide products obtained by ozonolysis of olefins in tetrahydrofuran gives mainly carboxylic acids and their derivatives.
- Ishmuratov,Legostaeva,Garifullina,Botsman,Muslukhov,Ishmuratova,Tolstikov
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p. 928 - 933
(2014/10/15)
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- Transformation of peroxide products of olefin ozonolysis under treatment with hydroxylamine and semicarbazide hydrochlorides in acetic acid
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Hydrochlorides of hydroxylamine and semicarbazide efficiently reduce peroxide products of olefin ozonolysis in a system CH2Cl2-AcOH leading to the formation of carboxylic acids and their derivatives. The application of water as the solvent component favors the increase in the fraction of nitrogen-containing organic compounds (semicarbazones, keto- and aldoximes, nitriles) and reduction in the yield of carboxylic acids.
- Ishmuratov,Legostaeva,Garifullina,Botsman,Muslukhov,Tolstikov
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p. 1075 - 1081
(2015/02/02)
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- Efficient synthesis of chiral Δ2-1,3,4-thiadiazolines from α-pinene and verbenone
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The synthesis of chiral cyclobutane 1,3,4-thiadiazoline derivatives starting from (-)-α-pinene and (-)-verbenone was studied. The diastereoisomeric excesses of the products obtained depended strongly upon the starting chiral ketone. The stereochemical assignments of the synthesized compounds were performed by NMR spectroscopy, X-ray analysis, and theoretical calculations.
- Sarmiento, Gabriela P.,Rouge, Pablo D.,Fabian, Lucas,Vega, Daniel,Ortuno, Rosa M.,Moltrasio, Graciela Y.,Moglioni, Albertina G.
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scheme or table
p. 1924 - 1929
(2012/01/13)
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- Tetrapropylammonium perruthenate catalyzed glycol cleavage to carboxylic (Di)acids
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A new method to accomplish glycol cleavage to carboxylic (di)acids in one step using catalytic amounts of tetrapropylammonium perruthenate (TPAP) together with N-methylmorpholine N-Oxide (NMO) as the stoichiometric oxidant is presented. In addition to regenerating the active catalyst, the N-oxide stabilizes intermediary carbonyl hydrates and thereby shifts a crucial equilibrium. The mild oxidation protocol is applicable to a broad range of substrates providing the respective acids, diacids, or keto acids in high yields.
- Schmidt, Andrea-Katharina C.,Stark, Christian B. W.
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supporting information; experimental part
p. 5788 - 5791
(2011/12/05)
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- 2-Azapinanes: Aza Analogues of the Enantiomeric Pinyl Carbocation Intermediates in Pinene Biosynthesis
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The enantiomeric 2-azapinanes, aza analogues of the pinyl carbocation intermediates in pinene biosynthesis, were synthesized from (-)-and (+)-cis-pinonic acids. The individual reactions in the 5-step sequence were Beckmann rearrangement of the pinonic acid oximes, cyclization to the N-acetyl lactams, hydrolysis to the NH-lactams, N-methylations, and LiAlH4 reductions. The anti stereochemistry of the N-methyl groups in the salts with respect to the gem-dimethyl bridge was established by NOE measurements and by X-ray diffraction analysis.(Figure Presented)
- Faraldos, Juan A.,Kariuki, Benson M.,Coates, Robert M.
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supporting information; scheme or table
p. 836 - 839
(2011/04/26)
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- Organic acid formation in the gas-phase ozonolysis of α-pinene
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The mechanism of formation of pinonic and norpinonic acids from α-pinene ozonolysis has been investigated by studying the products of the ozonolysis of an enone derived from α-pinene using gas chromatography coupled to mass spectrometry. the Owner Societies.
- Ma, Yan,Luciani, Thomas,Porter, Rachel A.,Russell, Andrew T.,Johnson, David,Marston, George
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p. 5084 - 5087
(2008/09/20)
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- Pinic and pinonic acid formation in the reaction of ozone with α-pinene
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The mechanism of formation of key compounds in atmospheric secondary aerosol (SOA) has been investigated by studying the products of the ozonolysis of an enal derived from α-pinene using gas chromatography coupled to mass spectrometry. The Royal Society of Chemistry.
- Ma, Yan,Willcox, Timothy R.,Russell, Andrew T.,Marston, George
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p. 1328 - 1330
(2008/01/01)
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- Prenylation inhibitors containing dimethylcyclobutane and methods of their synthesis and use
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The present invention is directed to compounds useful in the treatment of diseases associated with prenylation of proteins and pharmaceutically acceptable salts thereof, to pharmaceutical compositions comprising same, and to methods for inhibiting protein prenylation in an organism using the same.
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Page column 27
(2008/06/13)
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- Synthesis of two enantiomerically pure precursors of cyclobutane carbocyclic nucleosides
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Several bi-functionallized derivatives of cyclobutane have been synthesized by functional-group manipulation starting from (-)-cis-pinonic acid as a common precursor, the configuration of the pre-existing and newly formed stereogenic centers being determined by the configuration of the starting material, commercially available (-)-1S-α-pinene. Final products, (+)-(1S,1′R)-cis-1-[3′-(aminomethyl)-2′,2′- dimethylcyclobutyl]ethanol 5 and (+)-(1S,1′R)-cis-1-[3′-(2″- aminoethyl)-2′,2′-dimethylcyclobutyl]ethanol 6 are useful as precursors to cyclobutane carbocyclic nucleosides.
- Hergueta, Antonio R.,Lopez, Carmen,Fernandez, Franco,Caamano, Olga,Blanco, Jose M.
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p. 3773 - 3778
(2007/10/03)
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- A structural and mechanistic investigation of the mono-O-phenylation of diols with BiPh3(OAc)2
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The mono-O-phenylation of enantiomerically pure pinanediol 2 using BiPh3(OAc)2 1 and the biphenyl-2,2′-ylenephenylbismuth analogue 9 has been investigated. It is postulated that reductive elimination at the trigonal bipyramidal bismuth (V) centre of 1 upon exposure to ambient light affects the transfer of an apical phenyl ligand to the least sterically encumbered hydroxyl group of the diol, affording the monophenyl ether in good yield. SbPh3(OAc)2 fails to undergo reductive elimination, affording the stable diolate 6 instead. The X-ray crystal structure of 6 provides a reasonable model for the intermediate of the bismuth mono-O-phenylation, and suggests further studies with bismuth complexes such as 9 possessing intramolecularly tethered ligands incapable of facilitating the mono-O-phenylation reaction. The discussions are supported by X-ray crystallographic correlations, and calculations indicate that (M)-(-)-6 adopts the lowest energy conformational diastereoisomer.
- Coles, Simon J,Costello, James F,Hursthouse, Michael B,Smith, Stephen
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- An analytical approach for a comprehensive study of organic aerosols
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Unknown products identified precisely: The coupling of liquid chromatography to NMR spectroscopy, mass spectrometry, and infrared spectroscopy and the use of high-resolution mass spectrometry is utilized to investigate the formation of atmospheric-relevan
- Schrader, Wolfgang,Geiger, Jutta,Godejohann, Markus,Warscheid, Bettina,Hoffmann, Thorsten
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p. 3998 - 4001
(2007/10/03)
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- Modified cyclobutane carbonucleosides: Synthesis and evaluation of their antiviral activity
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The synthesis of some 9-(2-cyclobutylethyl)guanine derivatives and analogous carbonucleosides from 1 S-α-pinene is here presented. None of them showed detectable selectivity when assayed in the performed anti-viral tests.
- Fernandez,Hergueta,Lopez,De Clercq,Balzarini
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p. 1129 - 1131
(2007/10/03)
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- Carboxylic acids in secondary aerosols from oxidation of cyclic monoterpenes by ozone
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A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e. dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1 (cis-3- carboxy-2,2-dimethylcyclobutylethanoic acid) from α-and β-pinene; cis- pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis- 10-hydroxypinonic acid AB6 (cis-2,2-dimethyl-3- hydroxyacetylcyclobutylethanoic acid) from α-pinene and β-pinene; cis-3- caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3- caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3-(hydroxy-2- oxopropyl)cyclopropanylethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6- oxo-heptanoic acid), 7-hydroxylimononic acid L6 (3-isopropenyl-7-hydroxy-6- oxoheptanoic acid), and 7-hydroxylimononic acid L6' (7-hydroxy-3-isopropenyl- 6-oxoheptanoic acid) from limonene. A series of smog chamber experiments have been conducted in which five cyclic monoterpenes were oxidized by ozone. The evolved secondary aerosol was analyzed by GC-MS and HPLC-MS for nonvolatile polar oxidation products with emphasis on the identification of carboxylic acids. Three classes of compounds were determined at concentration levels corresponding to low percentage molar yields: i.e. dicarboxylic acids, oxocarboxylic acids, and hydroxyketocarboxylic acids. Carboxylic acids are highly polar and have lower vapor pressures than their corresponding aldehydes and may thus play an important role in secondary organic aerosol formation processes. The most abundant carboxylic acids were the following: cis-pinic acid AB1 (cis-3-carboxy-2,2-dimethylcyclobutylethanoic acid) from α- and β-pinene; cis-pinonic acid A3 (cis-3-acetyl-2,2-dimethylcyclobutylethanoic acid) and cis-10-hydroxypinonic acid AB6 (cis-2,2-dimethyl-3-hydroxyacetylcyclobutyl-ethanoic acid) from α-pinene and β-pinene; cis-3-caric acid C1 (cis-2,2-dimethyl-1,3-cyclopropyldiethanoic acid), cis-3-caronic acid C3 (2,2-dimethyl-3-(2-oxopropyl)cyclopropanylethanoic acid), and cis-10-hydroxy-3-caronic acid C6 (cis-2,2-dimethyl-3-(hydroxy-2-oxopropyl)cyclopropanyl-ethanoic acid) from 3-carene; cis-sabinic acid S1 (cis-2-carboxy-1-isopropylcyclopropylethanoic acid) from sabinene; limonic acid L1 (3-isopropenylhexanedioic acid), limononic acid L3 (3-isopropenyl-6-oxo-heptanoic acid), 7-hydroxy-limononic acid L6 (3-isopropenyl-7-hydroxy-6-oxoheptanoic acid), and 7-hydroxylimononic acid L6′ (7-hydroxy-3-isopropenyl-6-oxoheptanoic acid) from limonene.
- Glasius, Marianne,Lahaniati, Maria,Calogirou, Aggelos,Di Bella, Dario,Jensen, Niels R.,Hjorth, Jens,Kotzias, Dimitrios,Larsen, Bo R.
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p. 1001 - 1010
(2007/10/03)
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- Divergent routes to chiral cyclobutane synthons from (-)-α-pinene and their use in the stereoselective synthesis of dehydro amino acids
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Several polyfunctionalized cyclobutane derivatives have been synthesized using commercial (-)-α-pinene and (-)-verbenone as chiral precursors. Thus, oxidative cleavage of these compounds by using ruthenium trichloride afforded quantitatively (-)-cis-pinonic and (-)-cis-pinononic acids, respectively, without epimerization. These products were converted into several types of aldehydes, which are the key intermediates in the synthesis of cyclobutane dehydro amino acids via Wittig-Horner condensations with suitable phosphonates. These reactions are highly stereoselective, affording exclusively (Z) isomers, stereochemistry being assessed by NMR experiments. The obtained dehydro amino acids are polyfunctionalized molecules useful for the synthesis of other α-amino acids, with additional chiral centers, whose configuration must be induced by the chirality of the terpene employed as a precursor.
- Moglioni,Garcia-Exposito,Aguado,Parella,Branchadell,Moltrasio,Ortuno
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p. 3934 - 3940
(2007/10/03)
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- Ozonides of mono-, bi- and tricyclic terpenes
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Ozonolysis of (+)-limonene (1) afforded a monoozonide 2 by attack of ozone at the internal double bond and two diastereomeric diozonides (3). Ozonolysis of 1 on polyethylene gave diozonides 3, and ozonolysis on silica gel gave an epoxy ozonide 5. Ozonolyses of (-)-β-pinene (15), (+)-sabinene (20) and (+)-aromadendrene (23) gave two diastereomers, each, of the corresponding ozonides 16, 21 and 24, respectively. Ozonolysis of camphene (26) gave a very labile ozonide 27, while ozonolysis of (-)-α-pinene (12) gave no ozonide. Ozonolysis of (+)-limonene (1) in the presence of formaldehyde gave a cross-ozonide (4), derived from ozone cleavage of the internal double bond, and ozonolysis of (-)-β-pinene in the presence of acetaldehyde also gave a cross-ozonide (17).
- Griesbaum, Karl,Hilss, Michael,Bosch, Joachim
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p. 14813 - 14826
(2007/10/03)
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- Crystal Sturcture and Direction of the Polar Axis of (-)-(!S)-Pionic Acid β-Oxime
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(-)-(1S)-cis-3-(Hydroxyiminoethyl)-2,2-dimethyl-cyclobutylacetic acid, C10H17NO3, Mr=199.25, monoclinic, P21, a=14.632(8), b=12.193(3), c=7.103(2)A, β=112.54(3) deg, V=117O.5(8)A3, Z=4 (two independent molecules in the asymmetric unit), Dx=1.130 g/cm3, MoKα, λ=0.7l073 A, μ=0.69 1/cm, F(000)=432, T=295 K, R=0.047 for 1156 observed reflecitons 2.5?(i)> and 257 parameters.Calculation suggests that he polarization of molecules of the (-)-enantiomer, oriented as in the crystal, is such that the positive end of the crystal's electric dipole is toward the + end of the b axis; conversely, for the (+)-enantiomer the polarization is in the opposite sense with the electrically positive end of the crystal dipole toward -b.This electrical polarization, due to te molecular orientation found from the crystal structure determination of the crystal produced by heating (the pyroelectric effect) as determined by the Kundt-Buerker powder test.Thus, as has been found in previous examples, the orientation along the polar axis of the electric dipole induced by heating is the same as the orientation of the polarization of the crystal deduced from the X-ray structure.
- Padmanabhan, K.,Paul, I. C.,Curtin, D. Y.
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p. 411 - 415
(2007/10/02)
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- PHOTOCHEMICAL CYCLOBUTANONE EXPANSIONS
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As a model for a new approach to bond formation at anomeric carbons, the addition of various heteroatom derivatives to oxacarbenes generated by the photochemical ring expansion of cyclobutanones has been examined.Practical procedures have been developed for the insertion of such carbenes into heteroatom-H bonds from alcohols, thiols, and amines using minimal excess trapping reagent.
- Pirrung, Michael C.,DeAmicis, Carl V.
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p. 189 - 192
(2007/10/02)
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