4276-46-4Relevant academic research and scientific papers
Aliphatic C-H activation with aluminium trichloride-acetyl chloride: Expanding the scope of the Baddeley reaction for the functionalisation of saturated hydrocarbons
Lyall, Catherine L.,Uosis-Martin, Mario,Lowe, John P.,Mahon, Mary F.,Panto?, G. Dan,Lewis, Simon E.
supporting information, p. 1468 - 1475 (2013/05/21)
The functionalisation of decalin by means of an "aliphatic Friedel-Crafts" reaction was reported over fifty years ago by Baddeley et al. This protocol is of current relevance in the context of C-H activation and here we demonstrate its applicability to a range of other saturated hydrocarbons. Structural elucidation of the products is described and a mechanistic rationale for their formation is presented. The "aliphatic Friedel-Crafts" procedure allows for production of novel oxygenated building blocks from abundant hydrocarbons and as such can be considered to add significant synthetic value in a single step.
Why a proximity-induced Diels-Alder reaction is so fast
Krenske, Elizabeth H.,Perry, Emma W.,Jerome, Steven V.,Maimone, Thomas J.,Baran, Phil S.,Houk
scheme or table, p. 3016 - 3019 (2012/10/07)
Unlike normal Diels-Alder reactions of acyclic alkadienes with alkenes, the vinylbicyclo[2.2.2]octene employed in the Baran total synthesis of vinigrol undergoes a quantitative Diels-Alder reaction with a tethered alkene at room temperature. Density functional theory calculations reveal that this unprecedented reactivity originates from a combination of preorganization, diene strain, and tether stabilization.
Reduction of alkyl and vinyl sulfonates using the CuCl2· 2H2O-Li-DTBB(cat.) system
Radivoy, Gabriel,Alonso, Francisco,Moglie, Yanina,Vitale, Cristian,Yus, Miguel
, p. 3859 - 3864 (2007/10/03)
The reduction of a series of alkyl mesylates, dimesylates and triflates to the corresponding hydrocarbons was efficiently performed using a reducing system composed of CuCl2·2H2O, an excess of lithium sand and a catalytic amount (5 mol%) of 4,4′-di-tert-butylbiphenyl (DTBB), in tetrahydrofuran at room temperature. The process was also applied to enol and dienol triflates affording alkenes and dienes, respectively. The use of the deuterated copper salt CuCl2·2D2O allowed the simple preparation of the corresponding deuterated products.
The effect of pressure on cyclizations. The ring-size dependent reaction volumes of the cyclization of 1-alkenes to cycloalkanes. Experimental measurement of activation and reaction volumes of the intramolecular diels - Alder reaction of 1,3,8-nonatriene and 1,3,9-decatriene. Temperature dependence of activation and reaction volumes
Diedrich, Matthias K.,Kl?rner, Frank-Gerrit
, p. 6212 - 6218 (2007/10/03)
The volumes of reaction determined for the hypothetical cyclization of 1-alkenes to cycloalkanes decrease continUOusly from the formation of cyclopropane (ΔV(R) = -5.5 cm3 mol-1) up to the formation of cyclodecane (ΔV(R) = -32.3 cm3 mol-1) and seem to be constant for the larger rings. The analysis of the packing coefficients (η = V(w)/V) leads to the conclusion that this ring-size dependent decrease in volume results from the different packing of cyclic and acyclic compounds rather than from the changes in their intrinsic molecular volumes. The investigation of the intramolecular Diels-Alder reactions of (E)-l,3,8-nonatriene (E)-1 and (E)- 1,3,9-decatriene (E)-2 leading to the bicyclo[4.3.0]nonenes cis- and trans-4 (ΔV≠/ΔV(R) [cm3 mol-1] -24.8/-32.0 and -24.8/-28.5, respectively) or bicyclo[4.4.0]decenes cis- and trans-6 (-37.6/-45.4 and -35.0/-37.4, respectively) confirms the ring-size dependence of the activation and reaction volumes. The dependence of the effect of pressure from the number of newly forming rings is illustrated with the thermolysis of (Z)-1,3,8- nonatriene (Z)-1 in which an intramolecular Diels-Alder reaction leading to bicyclo [4.3.0]nonene cis-4 competes with a sigmatropic [1,5] hydrogen shift leading to (E,Z)-1,5,7-nonatriene 7. The use of high pressure causes a reversal of selectivity.
Experimental determination of the activation parameters and stereoselectivities of the intramolecular Diels-Alder reactions of 1,3,8-nonatriene, 1,3,9-decatriene, and 1,3,10-undecatriene and transition state modeling with the Monte Carlo-Jumping between Wells/molecular dynamics method
Diedrich, Matthias K.,Kl?rner, Frank-Gerrit,Beno, Brett R.,Houk,Senderowitz, Hanoch,Still, W. Clark
, p. 10255 - 10259 (2007/10/03)
Experimental activation parameters for the intramolecular Diels-Alder reactions of 1,3,8-nonatriene, 1,3,9-decatriene, and 1,3,10-undecatriene have been measured, and the Monte Carlo-Jumping between Wells/Stochastic Dynamics [MC(JBW)/SD] method, which gives relative free energies of activation, was tested as a means to predict stereoselectivities. The predictions are compared to experimental results, and to predictions from quantum and molecular mechanics methods.
Singlet and Triplet Excited-state Formation in High-energy Electron Tracks in Liquid cis- and trans-Decalin as studied by Product Formation in Radiolysis and Photolysis
Hummel, A.,Leng, H. C. de,Luthjens, L. H.,Wojnarovits, L.
, p. 2459 - 2466 (2007/10/02)
The yields of products formed as a result of irradiation of liquid cis- and trans-decalin with γ-rays and 3 MeV electrons as well as with 7.6 eV photons have been determined by means of gas-liquid chromatography (GLC).The major products for both cis- and trans-decalin are hydrogen, unsaturated C10 products and dimers; in the case of cis-decalin, cis-trans isomerization takes place via a chain reaction.Singlet and triplet excited states are formed by direct excitation and by charge recombination in the tracks of high-energy electrons.The product formation resulting from the singlets is determined by the photolysis.From a knowledge of the total yield of singlets from the radiolysis, the contribution of the singlet excited states to product formation during radiolysis is calculated and the remaining products are assigned to the triplets.For the sum of the yields of singlets and triplets a value of 6.4 (100 eV)-1 (=6.6E-7 mol J-1) is found for cis-decalin and 6.0 (100 eV)-1 (=6.2E-7 mol J-1) for trans-decalin and for the singlet fractions 0.53 and 0.47 in cis- and trans-decalin, respectively.The probability of C-H bond breakage in the singlet and triplet states is 0.42 and 0.82, respectively, for cis-decalin and 0.50 and 0.94, respectively, for trans-decalin.
Synthesis of the Pyrroloisoquinoline Substructure of the Manzamine Family of Alkaloids
Hart, David J.,McKinney, Jeffrey A.
, p. 2611 - 2614 (2007/10/02)
The first synthesis of the tricyclic pyrroloisoquinoline substructure of manzamines A, B, E and F is described.Reductive alkylation of benzoic acid followed by a 3-aza-6-heptenyl radical cyclization gave octahydroisoquinoline 9.An electrophile init
Copper(II) Triflate, a New Reagent for Mild Dehydration of Alcohols: Synthetic Usefulness and Mechanistic Insight
Laali, Khosrow,Gerzina, Robert J.,Flajnik, Christine M.,Geric, Cynthia M.,Dombroski, Ann Marie
, p. 607 - 611 (2007/10/02)
The effectiveness of copper(II) triflate (copper(II) trifluoromethanesulfonate) as a new dehydrating reagent for a variety of alcohols has been demonstrated.Based on several control experiments, a possible mechanism is suggested.
THERMAL REARRANGEMENTS OF CYCLIC ALLENES via RETRO-ENE REACTIONS
Price, John D.,Johnson, Richard P.
, p. 2499 - 2502 (2007/10/02)
Flow vacuum thermolysis (500-650 deg C) of 1,2-cyclonona- and 1,2-cyclodecadienes yields, as primary products, terminal enynes and enedienes.Secondary intramolecular Diels-Alder reactions of the enedienes afford cis and trans bicyclics.
INTRAMOLECULAR DIELS-ALDER REACTIONS 1,3,8-NONATRIENE AND 1,3,9-DECATRIENE
Lin, Yi-Tsong,Houk, K. N.
, p. 2269 - 2272 (2007/10/02)
The stereoselectivites of the title reactions have been investigated from 140-340 deg C, and relative activation parameters for cis and trans product formation have been determined.
