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Sergei I Kozhushkov

Publications and source records attributed to Sergei I Kozhushkov.

At least 19 recordsLinked to original sources
PubMed2007

Stereoselective preparation of six diastereomeric quatercyclopropanes from bicyclopropylidene and some derivatives.

Diastereomeric meso- and d,l-bis(bicyclopropylidenyl) (5) were obtained upon oxidation with oxygen of a higher-order cuprate generated from lithiobicyclopropylidene (4) in 50 and 31 % yield, respectively. Their perdeuterated analogues meso-[D(14)]- and d,l-[D(14)]-5 were obtained along the same route from perdeuterated bicyclopropylidene [D(8)]-3 (synthesized in six steps in 7.4 % overall yield from [D(8)]-THF) in 20.5 % yield each. Dehalogenative coupling of 1,1-dibromo-2-cyclopropylcyclopropane (6) gave a mixture of all possible stereoisomers of 1,5-dicyclopropylbicyclopropylidene 16 in 69 % yield, from which (Z)-cis-16 was separated by preparative gas chromatography (26 % yield). The crystal structure of meso-5 looks like a superposition of the crystal structures of two outer bicyclopropylidene units (3) and one inner s-trans-bicyclopropyl unit, whereas the two outer cyclopropyl moieties adopt a gauche orientation with respect to the cyclopropane rings at the inner bicyclopropylidene units in (Z)-cis-16. Birch reduction with lithium in liquid ammonia of meso-5 and d,l-5 gave two pairs of diastereomeric quatercyclopropanes trans,trans-(R*,S*,R*, S*)-17/cis,trans-(R*,S*,R*,R*)-18 and trans,trans-(R*,S*,S*,R*)-19/cis,trans-(R*,S*,S*,S*)-20 in 97 and 76 % yield, respectively, in a ratio 9:1 for every pair. The latter diastereomer was also obtained as the sole product by Birch reduction of (Z)-cis-16 in 96 % yield. Under the same conditions, tetradecadeuterio analogues trans,trans-[D(14)]-(R*,S*,R*,S*)-17/cis,trans-[D(14)]-(R*, S*,R*,R*)-18 (8:1) and trans,trans-[D(14)]-(R*,S*,S*,R*)-19/cis,trans-[D(14)]-(R*,S*,S*,S*)-20 (12:1) were prepared from meso-[D(14)]-5 and d,l-[D(14)]-5 in 37 and 63 % yield, respectively. Reduction of meso-5 with diimine gave the cis,cis-quatercyclopropane (S*,S*,R*,R*)-21 as the main product (58 % yield) along with the cis,trans-diastereomer (S*,S*,R*,S*)-18 (29 % yield). Thus, five of the six possible diastereomeric quatercyclopropanes were obtained from meso-5, d,l-5, and (Z)-cis-16. The X-ray crystal structure analyses of trans,trans-(R*,S*,R*,S*)-17 and cis,cis-(S*,S*,R*,R*)-21 revealed for the both an unusual conformation in which the central bicyclopropyl unit adopts an s-trans-(antiperiplanar) orientation with phi=180.0 degrees , and the two terminal bicyclopropyl moieties adopt a synclinal conformation with phi=49.8 and 72.0 degrees , respectively. In solution the vicinal coupling constants (3)J(H,H) in trans,trans-(R*,S*,R*,S*)-[D(14)]-17, trans,trans-(R*,S*,S*,R*)-[D(14)]-19, trans,cis-(R*,S*,R*,R*)-[D(14)]-18 and trans,cis-(R*,S*,S*,S*)-[D(14)]-20 were found to be 4.1, 4.7, 5.9 and 5.9 Hz, respectively. This indicates a predominance of the all-gauche conformer in (R*,S*,R*,S*)-17 and a decreasing fraction of it in this sequence of the other diastereomers.

Computer Simulation↗
PubMed2006

Syntheses and properties of enantiomerically pure higher (n > or = 7) [n-2]triangulanedimethanols and sigma-[n]helicenes.

(P)-(+)-Hexaspiro[2.0.0.0. 0.0.2.1.1.1.1.1]pentadecane [(P)-17] as well as (M)-(-)- and (P)-(+)-octaspiro[2.0.0.0.0.0.0.0.2.1.1.1.1.1.1.1]nonadecanes [(M)- and (P)-25]-enantiomerically pure unbranched [7]- and [9]triangulanes-have been prepared starting from racemic THP-protected (methylenecyclopropyl)methanol 6. The relative configurations of all important intermediates as well as the absolute configurations of the key intermediates were established by X-ray crystal structure analyses. This new convergent approach to enantiomerically pure linear [n]triangulanes for n=7, 9 was also tested in two variants towards [15]triangulane. Some of the most prominent and unexpected features of the newly prepared compounds are the remarkable modes of self-assembly of the diols (P)-14, (E)-(3S,3'S,4S,4'S,5R,5'R)-21, (P)-(+)-22, and (E)-31 in the solid state through frameworks of intermolecular hydrogen bonds leading to, depending on the respective structure, nanotube- [(P)-14, (P)-(+)-22, and (E)-31], honeycomb-like structures [(E)-(3S,3'S,4S,4'S,5R,5'R)-21] or a supramolecular double helix [(P)-(+)- and (M)-(-)-22]. Liquid crystalline properties of the esters and ethers of the diols (P)-14, (P)-, and (M)-22 have also been tested. Although all of these [n]triangulanes have no chromophore which would lead to significant absorptions above 200 nm, they exhibit surprisingly high specific rotations even at 589 nm with [alpha](20)(D)=+672.9 (c=0.814 in CHCl(3)) for (P)-(+)-17, +909.9 (c=0.96 in CHCl(3)) for (P)-(+)-25, -890.5 (c=1.01 in CHCl(3)) for (M)-(-)-25, and -1302.5 (c=0.36 in CHCl(3)) for (M)-(-)-39, and the specific rotations increase drastically on going to shorter wavelengths. This outstanding rotatory power is in line with their rather rigid helical arrangement of sigma bonds, and accordingly these helically shaped unbranched [n]triangulanes may be termed "sigma-[n]helicenes", as they represent the sigma-bond analogues of the aromatic pi-[n]helicenes. Density functional theory (DFT) computations at the B3 LYP/6-31+G(d,p) level of theory for the geometry optimization and time-dependent DFT for determining optical rotations with a triplet-zeta basis set (B3 LYP/TZVP) reproduce the optical rotatory dispersions (ORD) very well for the lower members (n=4, 5) of the sigma-[n]helicenes. For the higher ones (n=7, 9, 15) the computed specific rotations turn out increasingly larger than the experimental values. The remarkable increase of the specific rotation with an increasing number of three-membered rings is proportional neither to the molecular weight nor to the number of cyclopropane rings in these sigma-[n]helicenes.

Journal Article↗
PubMed2006

Syntheses and structures of sterically congested linear and branched cobalta[n]triangulanes.

Treatment of {eta(5):eta(1)[2-(di-tert-butylphosphanyl-P)ethyl]cyclopentadienyl}cobalt(I) chloride (5) with methylenecyclopropane (3) or bicyclopropylidene (4), as well as with their spirocyclopropanated analogues methylenespiropentane (7), cyclopropylidenespiropentane (10), or 7,7'-bi(dispiro[2.0.2.1]heptylidene) (15) in the presence of sodium amalgam at -50 degrees C, furnished the stable cobalt complexes 6, 9, 8, 11, and 16, respectively, in 72, 83, 84, 86, and 54 % isolated yield, respectively. The complexes 14 and 16 were also obtained by ligand exchange of the ethene complex {eta(5):eta(1)[2-(di-tert-butylphosphanyl-P)ethyl]cyclopentadienyl}(eta(2)-ethene)cobalt(I) (12) with 13 and 15 in 79 and 52 % yield, respectively. The X-ray crystal-structure analyses of complexes 9, 14, and 16, as well as the NMR-spectroscopic data of all complexes, reveal that they can be regarded as linear and branched cobalta[n]triangulanes. The thermal stability of complexes 6, 8, and 9 up to 109, 145, and 160 degrees C was determined by differential thermal analysis-thermogravimetry (DTA-TG) analysis.

Journal Article↗
PubMed2006

Synthesis of enantiopure indolizinones by cascade ring enlargements of 4'-chlorospiro[cyclopropane-1,5'-isoxazolidines].

2-Chloro-2-cyclopropylideneacetates (1-Me and 1-Et) and their spiropentane analogues 2 cycloadd enantiopure five-membered cyclic nitrones to give the corresponding adducts (quantitatively, four examples), which undergo cascade ring enlargements to yield indolizinone derivatives (53-70%, four examples). The ring enlargement process is triggered by the abstraction of a bridgehead proton induced by a base and can be suppressed by the presence of a bulky substituent nearby, such as a (triisopropylsilyl)oxy group.

Cyclization↗
PubMed2006

Radical cations from dicyclopropylidenemethane and its octamethyl derivative.

The radical cations of dicyclopropylidenemethane (2) and its octamethyl derivative (2-Me8) are prone to rearrangements into those of (2-methylallylidene)cyclopropane (2a) and its octamethyl derivative (2a-Me8), respectively, by opening one three-membered ring. In contrast to the radical cations of bicyclopropylidene (1) and its octamethyl derivative (1-Me8), 2*+ and 2-Me8*+ are stable to opening of the second ring, because in this case the resulting species would be a non-Kekulé hydrocarbon with a quartet ground state. Similarly to 1, octamethyl substitution in 2 promotes the tendency to rearrangement. Thus, ESR and ENDOR studies indicate that the primary radical cation 2*+, which is formed upon gamma-irradiation of 2 in a CFCl3 matrix at 77 K, does not rearrange up to 150 K. On the other hand, when 2-Me8 is treated in the same way, only the rearranged radical cation 2a-Me8*+ can be observed and characterized by its ESR and ENDOR spectra. Nevertheless, the existence of the two "missing" species, 2a*+ and 2-Me8*+, is revealed by other methods. According to UV and IR studies, X irradiation of 2 in an Ar matrix leads directly to the ring-opened radical cation 2a*+. Moreover, magnetic field effects on the decay of fluorescence, which appears upon recombination of the radical anion of p-terphenyl with a radical cation generated from 2-Me8 in liquid octane, strongly suggest that 2-Me8*+ (and not 2a-Me8*+) is formed initially. From the temperature dependence of the decay, the activation energy of the ring-opening process 2-Me8*+ --> 2a-Me8*+ is estimated. The radical cations 2a*+ and 2a-Me8*+ are formally distonic with the spin residing in the allylic moiety and the charge accommodated on the central carbon atom of the allene pi-system. The intact cyclopropylidenemethylidene moiety assumes a "bisected" conformation, thus favoring an optimal interaction with the positively charged center on the pi-system.

Journal Article↗
PubMed2005

Linear and branched phospha[n]triangulanes.

Novel, highly stable, linear and branched mono- and diphospha[n]triangulanes were synthesized in high yields by the CuCl-catalyzed phosphinidene addition to spirocyclopropanated methylenecyclopropanes and bicyclopropylidenes. The effect of spirofusion on the electronic properties of these esthetically attractive phosphacycles is apparent from X-ray single crystal structure analyses, which reveals a tightening of the phosphirane ring on additional spirocyclopropanation, and from the NMR features that show deshielded chemical shifts for the ring-phosphorus and -carbon atoms. Steric factors play a role in the addition reaction when the substrate alkene carries a second sphere of spirocyclopropane rings and causes the formation of 2-phosphabicyclo[3.2.0]heptenes in small amounts. These by-products most probably result from addition of the [PhP(Cl)W(CO)(5)]-Cu-L (L=alkene or solvent) reagent to the spirocyclopropanated bicyclopropylidene to give an intermediate sigma-complex, which subsequently, facilitated by steric factors, undergoes a cyclopropylcarbinyl to cyclobutyl ring expansion followed by a [1,3]-sigmatropic shift.

Magnetic Resonance Spectroscopy↗
PubMed2005

Preparation and reactivity of [D3d]-octahedrane: the most stable (CH)12 hydrocarbon.

The synthesis of the (CH)12 hydrocarbon [D(3d)]-octahedrane (heptacyclo[6.4.0.0(2,4).0(3,7).0(5,12).0(6,10).0(9,11)]dodecane) 1 and its selective functionalization retaining the hydrocarbon cage is described. The B3LYP/6-311+G* strain energy of 1 is 83.7 kcal mol(-1) (4.7 kcal mol(-1) per C-C bond) which is significantly higher than that of the structurally related (CH)16 [D(4d)]-decahedrane 2 (75.4 kcal mol(-1); 3.1 kcal mol(-1) per C-C bond) and (CH)20 [I(h)]-dodecahedrane 3 (51.5 kcal mol(-1); 1.7 kcal mol(-1) per C-C bond); the heats of formation for 1-3 computed according to homodesmotic equations are 52, 35, and 4 kcal mol(-1). Catalytic hydrogenation of 1 leads to consecutive opening of the two cyclopropane rings to give C2-bisseco-octahedrane (pentacyclo[6.4.0.0(2,6).0(3,11).0(4,9)]dodecane) 16 as the major product. Although 1 is highly strained, its carbon skeleton is kinetically quite stable: Upon heating, 1 does not decompose until above 180 degrees C. The B3LYP/6-31G* barriers for the S(R)2 attack of the tBuO. and Br3C. radicals on a carbon atom of one of the cyclopropane fragments (Delta(298) = 27-28 kcal mol(-1)) are higher than those for hydrogen atom abstraction. The latter barriers are virtually identical for the abstraction from the C1-H and C2-H positions with the tBuO. radical (DeltaG(298) = 17.4 and 17.9 kcal mol(-1), respectively), but significantly different for the reaction at these positions with the Br3C. radical (DeltaG(298) = 18.8 and 21.0 kcal mol(-1)). These computational results agree well with experiments, in which the chlorination of 1 with tert-butyl hypochlorite gave a mixture of 1- and 2-chlorooctahedranes (ratio 3:2). The bromination with carbon tetrabromide under phase-transfer catalytic (PTC) conditions (nBu4NBr/NaOH) selectively gave 1-bromooctahedrane in 43 % isolated yield. For comparison, the PTC bromination was also applied to 2,4-dehydroadamantane yielding 54 % 7-bromo-2,4-dehydroadamantane.

Journal Article↗
PubMed2005

Intramolecular Pauson-Khand reactions of methylenecyclopropane and bicyclopropylidene derivatives as an approach to spiro(cyclopropanebicyclo[n.3.0]alkenones).

The trimethylsilyl-protected enynes 9a-c and 14a,b with alkynyl substituents on the three-membered ring or on the double bond of a methylenecyclopropane or a bicyclopropylidene moiety were prepared in two steps from the alcohols 6a-c and 12a,b, respectively, by conversion to the iodides and their coupling with lithium (trimethylsilyl)acetylide (8) in 38-73% overall yields. The bicyclopropylidene derivative 9d was synthesized in 49% yield directly from bicyclopropylidene (3) by lithiation followed by coupling with (5-iodopent-1-ynyl)trimethylsilane (11). Enynes 9b-d were protiodesilylated by treatment with K2CO3 in methanol to give the corresponding unprotected enynes 10b-d in 53, 74 and 94% yield, respectively. Enynes 17a-c with a carbonyl group adjacent to the acetylenic moiety were synthesized from oxo derivatives 15a-c by Wittig olefination followed by coupling with 8 in 47, 18 and 12% overall yield, respectively. Pauson-Khand reactions of the methylenecyclopropane derivatives with a substituent on the ring (9a,b and 10a) as well as on the double bond (14a,b and their in situ prepared protiodesilylated analogues) proceeded smoothly by stirring of the corresponding enyne with [Co2(CO)8] in dichloromethane at ambient temperature followed by treatment of the formed complexes with trimethylamine N-oxide under an oxygen atmosphere at -78 degrees C to give tricyclic or spirocyclopropanated bicyclic enones 18a,b, 19a, 20a,b, 21a,b in good yields. Alkynylbicyclopropylidene derivatives 9c,d and 10c,d formed the corresponding cobalt complexes at -78 to -20 degrees C. Treatment of the latter with N-methylmorpholine N-oxide under an argon atmosphere at -20 degrees C gave the spirocyclopropanated tricyclic enones 18c, 19c and 18d in 31-45% yields. The structure of 19c was proved by X-ray crystal structure analysis. The cyclization of enynones 17a-c in MeCN at 80 degrees C gave the spirocyclopropanated bicyclic diketones 22a-c in 38-65% yields. Intramolecular PKRs of the enynes 25a,d with a chiral auxiliary adjacent to the triple bond gave the corresponding products 26a,d in 70 and 79% yield, respectively, as 5:1 and 8:1 mixtures of diastereomers, respectively. Addition of lithium dimethylcuprate or higher order cuprates to the double bond of the former furnished bridgehead-substituted bicyclo[3.3.0]octanones 27a-c in 57-86% yields. Protiodesilylation of 27a followed by acetal cleavage gave the enantiomerically pure spirocyclopropanated bicyclo[3.3.0]octanedione (1R,5R)- 29a with [alpha]D(20)=-148 (c=1.0 in CHCl3) in 55% overall yield.

Journal Article↗
PubMed2005

Bullvalene trisepoxide and its stereospecific rearrangement to 2,8,12-trioxahexacyclo[8.3.0.0(3,9)0(4,6)0(5,13)0(7,11)]tridecane: two new C3-symmetrical oligocycles with propeller chirality.

Epoxidation of bullvalene (1) with a neutralized solution of Oxone gave racemic trisepoxide rac-6 in 93 % isolated yield. Its structure was examined by X-ray crystallography. The two enantiomers of 6 were separated by preparative HPLC and exhibited specific rotations of [alpha](25)(D)= +160, [alpha](25)(365)= +567 (c=0.946, CHCl(3)) for the firstly eluted and [alpha](25)(D)= -157, [alpha](25)(365)= -554 (c=0.986, CHCl3) for the secondly eluted enantiomer of 6. The geometry of (+)-6 and the absolute configuration of (-)-6 were determined by X-ray crystal structure analysis and anomalous diffraction, respectively. According to this, (-)-6 possesses (3R,5S,7S,9R,11R,13S)- and (+)-6 has (3S,5R,7R,9S,11S,13R)-configuration. Upon treatment with BF(3)Et(2)O at -78 degrees C, trisepoxide rac-6 rearranges with retention of the skeletal three-membered carbocycle to give the cage trisether rac-8, as proved by X-ray crystal structure analysis, in virtually quantitative yield. Enantiomers of rac-8 were separated by preparative HPLC and exhibited specific rotations of [alpha](25)(D)= +49, [alpha](25)(365)= +170 (c=1.01, CHCl3) (firstly eluting) and [alpha](25)(D)= -46, [alpha](25)(365)= -160 (c=1.02, CHCl(3)) (secondly eluting enantiomer). The absolute configuration of (-)-8 was determined by anomalous diffraction to be (1R,3R,7R,9R,11R,13R). DFT computations at the TD-B3 LYP/6-31+G(d,p)//B3 LYP/6-31+G(d) level of theory for (3R,5S,7S,9R,11R,13S)-6 and (1R,3R,7R,9R,11R,13R)-8 predicted specific rotations of -206.7 and -83.4, respectively. Acid-catalyzed isomerization of the enantiomerically pure (+)-6 proceeded without racemization to give exclusively (-)-8, and (-)-6 provided only (+)-8. Thus, this isomerization occurs with ring opening of the three C--O bonds in the epoxide moieties in the alpha-position relative to the three-membered carbocycle rather than in the beta-position.

Journal Article↗
PubMed2004

Final elucidation of the absolute configuration of the signal metabolite hormaomycin.

The complete absolute configuration of hormaomycin 1 a has been established by HPLC and HPLC/MS experiments with appropriately derivatized 4-propylprolines, (2S,4S)-6 and (2R,4R)-6, as well as 4-(Z)-propenylprolines, cis-5 and trans-5, and also feeding experiments with enantiomerically pure samples of the deuterium-labeled 3-(2'-nitrocyclopropyl)alanine, (2S)-3,3-[D2]15 and (2S)-2,2'-[D2]15, and 4-(Z)-propenylproline 2',4-[D2]-(2S,4R)-5. The latter five amino acids were prepared for the first time and allowed one to unequivocally assign the hitherto unknown absolute configurations of the last four stereocenters in hormaomycin 1 a. As a bonus, some new information about the biosynthesis of this molecule has also been gathered.

Depsipeptides↗
PubMed2004

Branched phospha[7]triangulanes.

A highly strained, thermally stable (up to 150 degrees C) branched phospha[7]triangulane was synthesized from the second-generation bicyclopropylidene and transient phosphinidene [Ph-P=W(CO)5], followed by demetalation in refluxing xylene. Bulkier transient CuCl-alkene-complexed phosphinidene gave 2-phosphabicyclo-[3.2.0]hept-1(5)-ene as an additional product. The "outer sphere" spirocyclopropanes provide a stabilizing factor for both of these novel compounds.

Journal Article↗
PubMed2003

Heats of formation of [2.2]paracyclophane-1-ene and [2.2]paracyclophane-1,9-diene - an experimental study.

The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners.

Journal Article↗
PubMed2003

Preparation and properties of centrally bridgehead-substituted hexacyclo[4.4.0.02,1.03,5.04,8.07,9]decanes ("diademanes") and related (CH)10 hydrocarbons.

6-Trimethylsilyl- (1 b), 6-hydroxymethyl- (1 e), and 6-methyldiademane (1 f) have been prepared by irradiation of the corresponding snoutene derivatives, in 23, 2.8, and 17 % yields, respectively, together with the isomeric 1-trimethylsilyl- (10 b) and 1-methyldiademane (10 f) (8 and 2 % yields, respectively). The starting 4-trimethylsilyl- (9 b) and 4-(trimethylsilyloxymethyl)snoutene (9 d) were prepared from the correspondingly substituted cyclooctatetraenes 4 b and 4 c in several steps in 20 and 8 % overall yields, respectively. Upon heating, as well as under the conditions of gas-chromatographic separation, diademanes 1 b, 10 b, 1 f, and 10 f rearranged into the corresponding C10- and C1-substituted triquinacenes 3 b, 3 f, 11 b, and 11 f, respectively. Rough kinetic measurements of these rearrangements indicate some acceleration of the reaction caused by the presence of a methyl substituent and retardation by that of a trimethylsilyl substituent, relative to the parent diademane 1 a. At this insufficient precision, however, the activation energies (E(a)) of 29.0 and 28.1 kcal mol(-1), respectively, are essentially the same as that reported for 1 a (28.3 kcal mol(-1)). An X-ray crystal structure analysis of trimethylsilylsnoutene 9 b revealed a significant lengthening of the distal (with respect to the substituent) bond (1.534 versus 1.505 A) in the unsubstituted cyclopropane ring. In the substituted cyclopropane ring, the two proximal bonds are lengthened (1.530 A) and the distal bond is slightly shortened 1.492 A). This indicates a small, but significant electron-withdrawing effect of the trimethylsilyl group in 9 b. An X-ray crystal structure analysis of 6-hydroxymethyldiademane 1 e showed pronounced alternation of the bond lengths in the six-membered ring, with 1.494(4) between and 1.539(4) A within the three cyclopropane moieties, in close agreement with computations at different theoretical levels. This structural feature corroborates a predisposition of the tris-sigma-homobenzene skeleton of this molecule in the ground state to undergo the facile [sigma(2)(s) + sigma(2)(s) + sigma(2)(s)] cycloreversion to the triquinacene skeleton observed for the parent diademane 1 a, its derivative 1 b and 1 f, as well as for other tris-sigma-homobenzene derivatives.

Journal Article↗
PubMed2003

Conformational studies by dynamic NMR. 95. Rotation around the adamantyl-alkyl bond. Remote substituent effect on conformational equilibrium.

Restricted rotation has been observed by NMR spectroscopy at very low temperature in isopropyladamantane, 1-tert-butyl-3-isopropyladamantane, and 1,3-diisopropyladamantane. The barriers for the corresponding dynamic processes were also determined. In the case of the disubstituted adamantane derivatives, two and four conformers, respectively, were observed and they were assigned on the basis of the symmetry properties. The relative populations deviate from the statistical distribution.

Journal Article↗
PubMed2003

Delocalizations in sigma-radical cations: the intriguing structures of ionized [n]rotanes.

Highly symmetric aliphatic hydrocarbons such as D(4h)-[4]rotane do not necessarily have degenerate HOMOs. According to our predictions based on high-level computations, its radical cation should display a highly delocalized D(4h)-symmetric structure, in contrast to its Jahn-Teller distorted cousin, the radical cation of [3]rotane, which exists in two distonic localized forms with C(2v) and C(s) symmetry.

Journal Article↗
PubMed2002

Completely spirocyclopropanated macrocyclic oligodiacetylenes and their permethylated analogues: preparation and properties.

The acyclic dehydrotrimer (12) and -hexamer (28) of 1,1-diethynyl-2,2,3,3-tetramethylcyclopropane were prepared from 1-chloro-1-(trimethylsilylethynyl)-2,2,3,3-tetramethylcyclopropane (4) in six and nine steps, respectively, in 36 and 8 % overall yield, respectively, using Cadiot-Chodkiewicz or Hay coupling procedures as key steps. Mono-tert-butyldimethylsilyl (TBDMS) protection of the acyclic dehydrotrimer (20) and -hexamer (23) of 1,1-diethynylcyclopropane followed by Hay coupling and protiodesilylation furnished the acyclic dehydrohexamer (23) and -dodecamer (29) in 35 and 56 % overall yield, respectively. Subsequent cyclizing oxidative dimerization of 12 or cyclization of 28 using a modified Glaser protocol produced the first completely permethylspirocyclopropanated macrocyclic oligodiacetylene, compound 30 in 49 and 21 % yield, respectively. The cyclic dehydrohexa- (31) and dehydrododecamer (32) have been prepared from 23 and 29 in 49 and 7 % yield by applying the same protocol. The macrocycle 32 is particularly interesting in that it contains 60 carbon atoms in the inner ring, and indeed a decomposition mode consecutively cleaving off ethylene units from it as well as from 31 and tetramethylethylene from the permethylated exp-[6]rotane 30 has been proved by differential scanning calorimetry with evolved gas analysis. The thermal decomposition of these "exploding" [6]rotanes 31 and 30 set on at 100 and 135 degrees C, respectively, and release energies of 478 and 285 kcal. mol(-1), respectively, significantly more than the energy release of the explosive hexogen with 143 kcal mol(-1).

Journal Article↗