A short and stereoselective synthesis of highly substituted cyclopropanes from α,β-unsaturated carbonyl compounds with dichloromethyl p-tolyl sulfoxide

The reaction of the α-sulfinyl carbanion of dichloromethyl p-tolyl sulfoxide with a variety of α,β-unsaturated carbonyl compounds gave highly substituted cyclopropanes (up to five substituents) in good to high yields with high stereoselectivity.     

A short synthesis of α-allenic alcohols from α,β-unsaturated carbonyl compounds with dichloromethyl p-tolyl sulfoxide

The reaction of the α-sulfinyl carbanion of dichloromethyl p-tolyl sulfoxide with α,β-unsaturated carbonyl compounds gave 1-chlorocyclopropyl p-tolyl sulfoxides having a carbonyl group in good to high yields. The carbonyl groups in the products were reduced or treated with alkylmetals to give alcohols. Finally, the alcohols were treated with Grignard reagent to give α-allenic alcohols via the rearrangement of the cyclopropylmagnesium carbenoid intermediates, which were generated by the sulfoxide-magnesium exchange reaction, in good to high yields. This procedure provides a new method for a short synthesis of various α-allenic alcohols in two or three steps from relatively easily available α,β-unsaturated carbonyl compounds.     

Domain-based local pair natural orbital CCSD(T) calculations of strongly correlated electron systems: Examination of dynamic equilibrium models based on multiple intermediates in S1 state of photosystem II

ABSTRACT

Domain-based local pair natural orbital (DLPNO) coupled cluster single and double (CCSD) methods with perturbative triples (T) correction with NormalPNO were used to compute energies for twelve different S₁ structures of the CaMn₄O₅ cluster in the oxygen evolving complex (OEC) of photosystem II (PSII). The DLPNO-CCSD(T₀) calculations with TightPNO for the important six structures among them revealed that the right (R)-opened S_1XYZW structures were more stable than the corresponding left (L)-opened structures (X?=?O₍₅₎, Y?=?W2, Z?=?W1, and W?=?O₍₄₎) of CaMn₄O₅. The three different S₁ structures belonging to the R-opened type (S_1acca, S_1bbca, and S_1abcb, where O^2-?=?a, OH^-?=?b and H₂O?=?c) were found nearly degenerated in energy, indicating the possibility of the coexistence of different structures in the S₁ state. The DLPNO-CCSD(T₀) calculations with TightPNO supported the proposal of a dynamic equilibrium model based on the multi-intermediate structures for the S₁ state, which is also in agreement with EPR and other experimental and hybrid DFT computational results. Implications of the computational results are discussed in relation to scope and applicability of NormalPNO and TightPNO for the CCSD(T₀) calculations of strongly correlated electron systems such as 3d transition-metal complexes.     

Synthesis of jaspine B regioisomers through palladium-catalyzed stereoselective tetrahydrofuran formation: Insight into the ligand recognition of sphingosine kinases

We recently reported a structure-activity relationship study of 4-epi-jaspine B derivatives toward sphingosine kinase (SphK) and identified selective inhibitors of two SphK isoforms. In this study, we designed and synthesized jaspine B regioisomers on the basis of palladium-catalyzed tetrahydrofuran formation and late-stage cross metathesis reactions to investigate the influence of the substitution position of functional groups on SphK inhibition. Evaluation of the jaspine B regioisomers SphK inhibitory activities revealed that several of these compounds exhibited comparable SphK1/2 inhibitory potency to that of 4-epi-jaspine B.     

Formation of pseudo[3]rotaxanes containing calix-bis-crowns and secondary ammonium ions and their thermodynamic stabilities in a solution: preorganization by second macrocycle and nonallosteric behavior exhibited by large crown cavities

This Letter describes the formation of pseudo[3]rotaxanes containing calix[4]-bis-crowns, exhibiting a 1,3-alternate conformation and large crown cavities, and secondary ammonium ions. The first and second association constants of pseudo[3]rotaxane formation are moderate (K₁ = 175, K₂ = 100 M⁻¹) and are higher than that of the corresponding pseudo[2]rotaxane (K = 24 M⁻¹), consisting of a calix[4]-mono-crown and the same secondary ammonium ion.     

Role of the K 1 Meson in K 0 Photoproduction off the Deuteron

Neutral kaon photoproduction off the nucleon and deuteron has been reinvestigated by utilizing the new experimental data on both targets. An isobar model for elementary operator and impulse approximation for the reaction on the deuteron have been used. The available free parameters in the elementary model have been extracted from both elementary and deuteron data. In contrast to the elementary reaction, fitting the deuteron data requires an inclusion of weighting factor. The result indicates that the angular distribution of the elementary ${K^0\Lambda}$ process does not show backward peaking behavior.     

Solid‐phase incorporation of gaseous carbon dioxide into oxirane‐containing copolymers

Carbon dioxide was incorporated into poly(glycidyl methacrylate‐co‐methyl methacrylate) by a solid‐phase reaction, which transformed the pendent oxirane moieties into cyclic carbonate moieties, with quaternary ammonium halide catalysts. The incorporation of carbon dioxide into the copolymer led to soluble carbonate‐containing polymers, whereas the incorporation of carbon dioxide into the glycidyl methacrylate homopolymer produced an insoluble product. The copolymer composition, reaction temperature, and catalyst amount affected the incorporation efficiency and the side reaction that caused crosslinking. Effective incorporation was achieved under the following reaction conditions: the glycidyl methacrylate content was less than approximately 50%, the temperature was greater than the glass‐transition temperature, and the catalyst concentration was 1.5–6 mol %. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3812–3817, 2004     

Final-state hyperon-nucleon interaction in the inclusive K photoproduction from the deuteron

We calculate d(γ, K⁺) inclusive cross sections with the full inclusion of the final ΛN - ΣN interaction. Modern hyperon-nucleon forces and a recently updated production operator for the γ + N → K⁺ + Y process are used. Significant effects of the hyperon-nucleon final-state interaction have been found especially around the K⁺ΣN threshold.