13668-59-2Relevant articles and documents
A short synthesis of (-)-carbovir
Hildbrand,Troxler,Scheffold
, p. 1236 - 1240 (1994)
(-)-Carbovir ((-)-1) was synthesized via the cyclic carbonate 2 in four steps starting from enantiomerically enriched (-)-(s)-(cyclopent-2-enyl)methanol ((-)-3).
Production of oxygen-containing alicyclic compounds (by machine translation)
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Paragraph 0027-0032; 0034, (2020/04/24)
[Problem] to provide, in a one-step reaction synthesizes an alicyclic compound containing oxygen, high yield production of oxygen-containing compound is a cycloaliphatic. [Solution] one or more hydroxy or carbonyl group 2, or a hydroxyl group having the carbon number of 5 or more aliphatic carbonyl group 2 in accordance with one or more oxygen-containing compound, a basic catalyst is brought into contact with an oxygen-containing alicyclic compound by cyclodehydration reaction, oxygen-containing alicyclic compound. [Drawing] no (by machine translation)
Parallel and competitive pathways for substrate desaturation, hydroxylation, and radical rearrangement by the non-heme diiron hydroxylase AlkB
Cooper, Harriet L. R.,Mishra, Girish,Huang, Xiongyi,Pender-Cudlip, Marilla,Austin, Rachel N.,Shanklin, John,Groves, John T.
supporting information, p. 20365 - 20375 (2013/02/25)
A purified and highly active form of the non-heme diiron hydroxylase AlkB was investigated using the diagnostic probe substrate norcarane. The reaction afforded C2 (26%) and C3 (43%) hydroxylation and desaturation products (31%). Initial C-H cleavage at C2 led to 7% C2 hydroxylation and 19% 3-hydroxymethylcyclohexene, a rearrangement product characteristic of a radical rearrangement pathway. A deuterated substrate analogue, 3,3,4,4-norcarane-d 4, afforded drastically reduced amounts of C3 alcohol (8%) and desaturation products (5%), while the radical rearranged alcohol was now the major product (65%). This change in product ratios indicates a large kinetic hydrogen isotope effect of ～20 for both the C-H hydroxylation at C3 and the desaturation pathway, with all of the desaturation originating via hydrogen abstraction at C3 and not C2. The data indicate that AlkB reacts with norcarane via initial C-H hydrogen abstraction from C2 or C3 and that the three pathways, C3 hydroxylation, C3 desaturation, and C2 hydroxylation/radical rearrangement, are parallel and competitive. Thus, the incipient radical at C3 either reacts with the iron-oxo center to form an alcohol or proceeds along the desaturation pathway via a second H-abstraction to afford both 2-norcarene and 3-norcarene. Subsequent reactions of these norcarenes lead to detectable amounts of hydroxylation products and toluene. By contrast, the 2-norcaranyl radical intermediate leads to C2 hydroxylation and the diagnostic radical rearrangement, but this radical apparently does not afford desaturation products. The results indicate that C-H hydroxylation and desaturation follow analogous stepwise reaction channels via carbon radicals that diverge at the product-forming step.
Vapor-phase catalytic dehydration of terminal diols
Abe, Katsutoshi,Ohishi, Yusuke,Okada, Takuto,Yamada, Yasuhiro,Sato, Satoshi
experimental part, p. 419 - 424 (2012/02/03)
Vapor-phase catalytic reactions of several terminal diols were investigated over several rare earth oxides, such as Sc2O3, Y 2O3, CeO2, Yb2O3, and Lu2O3. Sc2O3 showed selective catalytic activity in the dehydration of terminal diols with long carbon chain, such as 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol, to produce the corresponding unsaturated alcohols. In the dehydration of 1,6-hexanediol, 5-hexen-1-ol was produced with selectivity over 60 mol%, together with by-products such as ε-caprolactone and oxacycloheptane. In the dehydration of 1,10-decanediol, 9-decen-1-ol was produced with selectivity higher than 70 mol%. In addition to Sc 2O3, heavy rare earth oxides such as Lu2O 3 as well as monoclinic ZrO2 showed moderate selectivity in the dehydration of the terminal diols.
Cage escape competes with geminate recombination during alkane hydroxylation by the diiron oxygenase AlkB
Austin, Rachel N.,Luddy, Kate,Erickson, Karla,Pender-Cudlip, Marilla,Bertrand, Erin,Deng, Dayi,Buzdygon, Ryan S.,Van Beilen, Jan B.,Groves, John T.
supporting information; experimental part, p. 5232 - 5234 (2009/04/04)
(Chemical Presented) AlkBstops the radical clock: Three structurally analogous radical-clock substrates with a large span in their rearrangement rates are hydroxylated by AlkB to afford similar amounts of rearranged (2) and unrearranged products (1). Such a result is in accord with radical rebound competing with cage escape of the geminate substrate radical. The results show that radical clocks can measure both the radical lifetime and the kinetics of cage escape.
Radical intermediates in monooxygenase reactions of Rieske dioxygenases
Chakrabarty, Sarmistha,Austin, Rachel N.,Deng, Dayi,Groves, John T.,Lipscomb, John D.
, p. 3514 - 3515 (2007/10/03)
Rieske dioxygenases catalyze the cis-dihydroxylation of a wide range of aromatic compounds to initiate their biodegradation. The archetypal Rieske dioxygenase naphthalene 1,2-dioxygenase (NDOS) catalyzes dioxygenation of naphthalene to form (+)-cis-(1R,2S
The diagnostic substrate bicyclohexane reveals a radical mechanism for bacterial cytochrome P450 in whole cells
Austin, Rachel N.,Deng, Dayi,Jiang, Yongying,Luddy, Kate,Van Beilen, Jan B.,Ortiz De Montellano, Paul R.,Groves, John T.
, p. 8192 - 8194 (2008/02/08)
(Figure Presented) On home ground: The reaction mechanisms of bacterial alkane-oxidizing cytochrome P450s were determined in their native environment using a novel diagnostic substrate probe, bicyclohexane, in whole cells and cell-free extracts (see picture). Purified P450cam also oxidizes bicyclohexane. Clear evidence for a substrate-based radical with a lifetime of 75-250 ps was obtained.
Regiochemical control of the ring opening of 1,2-epoxides by means of chelating processes. 9. Synthesis and ring opening reactions of cis- and trans-oxides derived from 3-(benzyloxymethyl)cyclopentene and methyl 2- cyclopenten-1-carboxylate
Colombini,Crotti,Di Bussolo,Favero,Gardelli,Macchia,Pineschi
, p. 8089 - 8112 (2007/10/02)
The regiochemical outcome of the ring opening of 1,2-epoxides through chelation processes assisted by metal ions, was verified in the oxirane systems derived from cyclopentene bearing a polar functionality (CH2OBn or COOMe) in a homoallylic relationship to the oxirane ring. The cis/trans diastereoisomeric epoxide pairs 7-8 and 9-10 derived from 3- (benzyloxymethyl)cyclopentene and methyl 2-cyclopenten-1-carboxylate, respectively, were prepared and some of their opening reactions were studied. The regioselectivity observed turned out to depend on the opening reaction protocol (standard or metal-assisted), suggesting the efficacious incursion, under the appropriate conditions, of chelate bidentate species in the opening process.
Homolytic Displacement at Saturated Carbon: Part 5. Synthesis of Cyclopropylmethyl, Bicyclohex-2-yl, Bicyclohept-2-yl and Cyclohexanespirocycloprop-2-yl Sulphones from the Corresponding But-3-enylcobaloximes
Gupta, B. Dass,Das, Indira,Dixit, Vandana
, p. 2409 - 2446 (2007/10/02)
But-3-enylcobaloxime reacts with arenesulphonyl chlorides under thermal and photochemical conditions to give cyclopropylmethyl sulphones.The yields depend upon the reaction conditions used.Similar reactions of cyclopent-2-enylmethylcobaloxime and cyclohex-2-enylmethylcobaloximes under photochemical conditions form a mixture of cis and trans isomers of bicyclohex-2-yl and bicyclohept-2-yl sulphones in (50:50) and (70:30) isomeric ratios respectively.However, cyclohex-3-enylcobaloximes form only the trans-bicyclohex-2-yl sulphone.Exclusive formation of cycloalkanespirocycloprop-2-yl sulphones is observed in the reactions of 2-(cyclo alk-1-enyl)ethylcobaloximes with arenesulphonyl chlorides.The reactions are free radical in nature and are believed to take place by a chain mechanism.In the key step a homolytic attack of the RSO2 radical at the terminal (δ) carbon of the butenyl ligand leads to the cyclized product.The exact nature of the ring closure step is uncertain, as both concerted and stepwise mechanisms are possible.
The Potential of Carbocyclic Nucleosides for the Treatment of AIDS: Synthesis of Carbocyclic 6'-Fluoro-2',3'-dideoxythymidine
Coe, Diane M.,Parry, David M.,Roberts, Stanley M.,Storer, Richard
, p. 2373 - 2378 (2007/10/02)
The carbocyclic nucleoside 4 and the corresponding triphosphate 5 were prepared from cyclopent-2-enylmethanol 6 in 8 and 10 steps respectively.The key step in the synthesis is the reaction of the azido alcohol 9 with diethylaminosulphur trifluoride: parti
