RESUMO
The conjugate addition of organocopper reagents to alpha, beta-unsaturated enones results in the regiospecific generation of enolate anions, which can be made to undergo the aldol reaction with (tetrahydropyranyloxy)acetaldehyde under zinc chloride catalysis. Treatment of the resulting product with p-toluenesulfonic acid in THF affords the targeted 2,3-disubstituted furan.
RESUMO
The N-(bromomethanesulfonyl) azabicyclic ketones 2a-c and their exo-methylene analogues 1a-c were prepared. Our examination of the radical-induced behavior of the latter triad provided experimental evidence for the propensity of the b and c systems to engage in 7-endo cyclization. For 1a, only reductive debromination was observed. In no instance was ring closure by the 6-exo radical mode seen. As concerns ketones 2a-c, all three showed a remarkable facility for engaging in intramolecular S(N)2 displacement in the presence of KHMDS. Yields at the mid-80% level were realized irrespective of the value of n. Molecular mechanics calculations of the Monte Carlo type were performed on several conformational isomers and product classes in an effort to provide support for the explanatory conclusions offered as rationale for the collective experimental observations.
RESUMO
[formula: see text] Addition of a very modest amount of lead tetraacetate (1.50 equiv relative to the amount of Grubbs catalyst) to ring-closing metathesis reaction mixtures effectively removes all colored ruthenium and phosphine impurities to deliver colories reaction products.
RESUMO
[formula: see text] An efficient strategy for the conversion of 1,2-diketones into saturated 1,6-diketones and delta 2,3/delta 3,4-unsaturated congeners thereof is reported.
RESUMO
[structure: see text] The C3V-symmetric triaxially locked trispirotetrahydrofuran 2 binds Li+ ions strongly and Na+ ions much less effectively. The observed discrimination factor is attributed to greater structural preorganiztion and lower solvation prior to selective complexation, and particularly to the formation of a 2:1 sandwich complex involving lithium. 13C NMR studies have defined a reluctance to form a 1:1 species when excess Li+ is present.
RESUMO
[structure: see text] Preparation of the first rigid homoditopic tris(tetrahydrofuranyl) ligand with a pair of exotopic binding sites specifically tailored for effective coordination to lithium ions is described. The crystallographically defined structural parameters of the monomeric building block and a 1:2 complex of the dimer with lithium picrate reveal the unique features of these materials.
RESUMO
The poly(spirotetrahydrofuranyl)cyclohexanes 1-4 were prepared in a series of steps that began with oxidative demercuration of pentaspirocyclic chloromercurials. Once the resulting alcohols were transformed into their ketones, it proved possible to cap this center with the Normant reagent and introduce the final heterocyclic ring. The cyclohexanones and the title compounds showed a strong tendency to project their C-O bonds equatorially to the maximum extent possible. The reluctance of these systems to participate in chair-to-chair conformational equilibration was made apparent during measurements to assess their coordination capability toward alkali metal ions. Although 3 was superior to its isomers, this polyether was overshadowed by 15 to an extent in excess of two powers of 10 in their relative capability to coordinate lithium cations. The synthesis, conformation, and low-level dynamic character of 5 are also detailed. To set the stereochemistry of the sixth spirotetrahydrofuranyl ring properly in this case, it was necessary to implement a novel strategy involving late-stage introduction of the oxygen atom. This protocol required intermediate formation of homoallylic alcohol 39, the epoxidation of which proceeded principally in the desired direction. X-ray crystallographic analysis of 5 established that the chair conformation which is adopted has all six C-O bonds projected equatorially. The total inability of 5 to bind to Li(+), Na(+), and K(+) denotes the existence of a substantial barrier to ring inversion. DNMR studies undertaken to assess the magnitude of this barrier demonstrated no change in high-field (1)H and (13)C line shapes up to 573K in 1, 3-([D(3)]methoxy)benzene. Consequently, 5 may qualify as the cyclohexane having the highest chair-chair conformational inversion barrier to the present time.
RESUMO
Despite the inherent preference for placing alkyl substituents, rather than alkoxy substituents, in equatorial positions, all-trans-hexaspiro(THF)cyclohexane strongly favors the all-O-equatorial conformer. Ab initio and density functional calculations on a series of cyclohexane derivatives containing one, two, or three spiro(THF) units demonstrate that this preference results from at least two important factors. First, when oxygen atoms are attached to adjacent carbons, the gauche effect favors the di-O-equatorial arrangement. In trans-1,2-dispiro(THF)cyclohexane, the single gauche interaction overcomes the inherent steric preference for projecting the two oxygen atoms axially. Similarly, in the all-trans-hexaspiro(THF)cyclohexane the six gauche interactions in the all-O-equatorial conformer overpower the inherent conformational biases of the six isolated spiro(THF) moieties. Nevertheless, the gauche effect only partially accounts for the more than 20 kcal/mol conformational bias calculated for this molecule. There is also another factor, the high energetic cost associated with projecting multiple alkoxy substituents axially on the same face of a cyclohexane scaffold. The calculations find the energetic cost of each 1,3-diaxial interaction is about 2 kcal/mol larger between alkoxy substituents than between alkyl substituents.
