New chiral phosphine-phosphite ligands in the enantioselective palladium-catalyzed allylic alkylation

A series of chiral phosphine-phosphite ligands 1-6 have been synthesized and used in the enantioselective palladium-catalyzed reaction of rac-1,3-diphenyl-2-propenyl acetate with dimethyl malonate as nucleophile. Ligands 1a, 2, 3, 5a, 6a, and 6b have been synthesized starting from racemic tert-butylphenylphosphinoborane. The use of dynamically resolved Li phosphide (-)-sparteine provided the optically pure ligands. Crystals of the allylpalladium (6a) complex were obtained, suitable for X-ray crystal structure determination. The X-ray crystal structure of the allylpalladium (6a) complex revealed a longer palladium-carbon bond distance trans to the phosphine moiety indicating that the attack of the nucleophile takes place at the carbon trans to the phosphine moiety. This was confirmed by the fact that the phosphine moiety did not affect the enantioselectivity directly. Under mild reaction conditions, enantioselectivities up to 83% were obtained (25 degrees C) with ligand 1e. Systematic variation of the ligand bridge and the phosphite moiety showed that the configuration of the product is controlled by the atropisomerism of the biphenyl substituent at the phosphite moiety. The conformation of the biphenyl group, in turn, is controlled by the substituent at the chiral carbon in the bridge. Ligands with large bite angles yielded higher enantioselectivities.     

Exact solution (within a double-zeta basis set) of the schrodinger electronic equation for water

Using recently developed theoretical techniques it has been possible to achieve an exact variational solution of the Schrödinger equation within a modest basis set or one-eleltron functions. The full configuration interaction for this system included a total of 256473 ¹A₁ spin-and space-adapted configurations. Comparison with many-body perturbation theory proves to be quite interesting.     

Aminosulf(ox)ides as ligands for Iridium(I)-catalyzed asymmetric transfer hydrogenation

A new class of efficient catalysts was developed for the asymmetric transfer hydrogenation of unsymmetrical ketones. A series of chiral N,S-chelates (6-22) was synthesized to serve as ligands in the iridium(I)-catalyzed reduction of ketones. Both formic acid and 2-propanol proved to be suitable as hydrogen donors. Sulfoxidation of an (R)-cysteine-based aminosulfide provided a diastereomeric ligand family containing a chiral sulfur atom. The two chiral centers of these ligands showed a clear effect of chiral cooperativity. In addition, aminosulfides containing two asymmetric carbon atoms in the backbone were synthesized. Both the sulfoxide-containing beta-amino alcohols and the aminosulfides derived from 1,2-disubstituted amino alcohols gave rise to high reaction rates and moderate to excellent enantioselectivities in the reduction of various ketones. The enantioselective outcome of the reaction was favorably affected by selecting the most appropriate hydrogen donor. Enantioselectivities of up to 97% were reached in the reduction of aryl-alkyl ketones.     

Towards curricular coherence in integers and fractions: a study of the efficacy of a lesson sequence that uses the number line as the principal representational context

This paper reports a study of the efficacy of Learning Mathematics through Representations (LMR), an innovative curriculum unit designed to support upper elementary students’ understandings of integers and fractions. The unit supports an integrated treatment of integers and fractions through (a) the use of the number line as a cross-domain representational context, and (b) the building of mathematical definitions in classroom communities that become resources to support student argumentation, generalization, and problem solving. In the efficacy study, fourth and fifth grade teachers employing the same district curriculum (Everyday Mathematics) were matched on background indicators and then assigned to either the LMR experimental classrooms (n = 11) or the comparison group (n = 8 with 10 classrooms). During the fall semester, LMR teachers implemented the LMR unit on 19 days and district curriculum on other days of mathematics instruction. HLM analyses documented greater achievement for LMR students than Comparison students on both the end-of-unit and the end-of year assessments of integers and fractions knowledge; the growth rates of LMR students were similar regardless of entering ability level, and gains for LMR students occurred on item types that included number line representations and those that did not. The findings point to the efficacy of the LMR sequence in supporting teaching and learning in the domains of integers and fractions.     

Exploiting rotational and translational invariance of the energy in derivative calculations in quantum chemistry

It is shown how the invariance of the Born—Oppenheimer potential energy to overall translations and rotations of a molecule can be used to reduce the computational labor required for derivative evaluations at various orders.     

A linear-time algorithm for computing the voronoi diagram of a convex polygon

We present an algorithm for computing certain kinds of three-dimensional convex hulls in linear time. Using this algorithm, we show that the Voronoi diagram ofn sites in the plane can be computed in (n) time when these sites form the vertices of a convex polygon in, say, counterclockwise order. This settles an open problem in computational geometry. Our techniques can also be used to obtain linear-time algorithms for computing the furthest-site Voronoi diagram and the medial axis of a convex polygon and for deleting a site from a general planar Voronoi diagram.This research began while the first and fourth authors were visiting the Mathematical Sciences Research Institute in Berkeley, California. Work by the fourth author was supported in part by NSF Grant No. 8120790.     

A Robust, Environmentally Benign Catalyst for Highly Selective Hydroformylation

By a sol-gel process a rhodium complex containing a diphosphane with a large natural P-Rh-P bite angle is covalently anchored in a silica matrix (see picture). The immobilized catalyst is a very selective hydroformylation catalyst that is completely and conveniently separated from the product and can be reused in numerous cycles.