Ethyl-4,4,4-trifluoroacetoacetate (ETFAA), a powerful building block for enantiopure chirons in trifluoromethyl-β-amino acid series

Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure.     

Formation of 2,6-dioxabicyclo[3.3.0]-octa-3,7-dienes or multiply substituted o-benzoquinones from reactions of 1,4-dilithio-1,3-dienes with dimethyl oxalate

Reactions of 1,4-dilithio-1,3-dienes with dimethyl oxalates afforded multiply substituted o-benzoquinones or stereodefined 2,6-dioxabicyclo[3.3.0]-octa-3,7-dienes in good yields.     

高阶微商系统Dirac猜想的一个反例

由扩展正则作用量导出了高阶微商奇异Lagrange量系统的扩展正则Noether恒等式.从广义约束Hamilton系统相空间中对称性分析，给出高阶微商系统Dirac猜想的一个反例. 用正则Noether定理、 正则Noether恒等式和扩展正则Noether恒等式说明在此反例中Dirac猜想失效, 讨论中没有将约束线性化. 关键词： 高阶微商系统 约束Hamilton系统 正则对称性 Dirac猜想     

Preparation of the conjugated polyene chains with the 1,4-dimethyl substitution

Allylic sulfones undergo the conjugate addition to diethyl chloroisopropylidenemalonate, followed by intramolecular cyclopropanation. DBU-promoted ring opening and subsequent desulfonation reactions of the resulting adduct produce the conjugated polyene chains with the 1,4-dimethyl substitution.     

On the Image Regularity Condition

In this paper, we continue the analysis of the image regularity condition (IRC) as introduced in a previous paper where we have proved that IRC implies the existence of generalized Lagrange-John multipliers with first component equal to 1. The term generalized is connected with the fact that the separation (in the image space) is not necessarily linear (when we have classic Lagrange-John multipliers), but it can be also nonlinear. Here, we prove that the IRC guarantees, also in the nondifferentiable case, the fact that 0 is a solution of the first-order homogeneized (linearized) problem obtained by means of the Dini-Hadamard derivatives.     

Symmetry specified enumeration of substituted derivatives: an easy solution to the complex problem

Several sophisticated methods to solution of symmetry specified enumeration problems are available in the modern literature. In this paper we propose a simple technique that allows one to manually compute the exact numbers of fixed-symmetry derivatives for a given structure either with inclusion or ignoring the substitution patterns. The basic idea of the method suggested consists in the derivation of Pólya-like cycle indices for the automorphism groups of specially constructed orbit partition graphs; the expansion of these indices and subsequent simple calculations result in the desired numbers of substituted derivatives with achiral substituents. Limitations of the new technique (and a method suggested earlier) depend on the relevance of the orbit partitions for particular subgroups of the point symmetry group. For illustration purposes, the results obtained for the prismane (D _3h ) and adamantane (T _d ) structures are discussed. In the former case the numbers of substituted derivatives can be found for all subgroups of the D _3h group, whereas in the latter case these numbers can be determined for eight out of eleven subgroups of the T _d point symmetry group. This work is based on the text of the lecture presented by the authors at the 5th All-Russia Conference on Molecular Modeling (Moscow, April 2007). The paper deals with the methodology and detailed treatment of applied aspects related to solution of enumeration problems for substituted derivatives with prescribed symmetry groups. Unlike the known methods of symmetry specified enumeration, the technique suggested is simple enough and may be regarded as generalization of the Pólya methodology, which is widely used by chemists. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 227–245, February, 2008.     

1-Benzopyran-4(4H)-ones as novel activated alkenes in the Baylis-Hillman reaction: a simple and facile synthesis of indolizine-fused-chromones

1-Benzopyran-4(4H)-one derivatives have been successfully employed as novel activated alkenes in the Baylis-Hillman coupling with heteroaromatic-aldehydes, nitrobenzaldehydes and isatin-derivatives and the corresponding adducts, derived from pyridine-2-carboxaldehyde, have been transformed into a novel indolizine-fused-chromone framework.     

Sugar conjugates of fulvestrant (ICI 182,780): efficient general procedures for glycosylation of the fulvestrant core

We have prepared glucose and cellobiose conjugates at the phenolic 3- and hydroxylic 17-positions of the pure anti-estrogenic compound fulvestrant (ICI 182,780), which has recently been approved in the USA for the treatment of advanced postmenopausal breast cancer. Glycosylation at the 17-position was achieved most effectively using pivaloyl protection of the sugar imidates employed, which we found suppressed the competing transacylation reaction and led to improved yields of the product glycosides.     

Crystallographic report: Crystal structure of 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide

For the unsymmetrical title compound, 1‐bromo‐1′‐[(2S)‐N‐(1‐hydroxy‐3‐methylbutane‐2‐yl)]‐ferroceneamide, two independent molecules were found in the asymmetric unit. Copyright © 2003 John Wiley & Sons, Ltd.