Organophotoredox/palladium dual catalytic decarboxylative Csp3–Csp3 coupling of carboxylic acids and π-electrophiles

A dual catalytic decarboxylative allylation and benzylation method for the construction of new C(sp³)–C(sp³) bonds between readily available carboxylic acids and functionally diverse carbonate electrophiles has been developed. The new process is mild, operationally simple, and has greatly improved upon the efficiency and generality of previous methodology. In addition, new insights into the reaction mechanism have been realized and provide further understanding of the harnessed reactivity.

A dual catalytic decarboxylative allylation and benzylation method for the construction of new C(sp³)–C(sp³) bonds between readily available carboxylic acids and functionally diverse carbonate electrophiles has been developed.     

A highly diastereoselective synthesis of 4-octulose and 2-deoxy-4-octulose from a -fructose derivative

Bishydroxylation of methyl

Full-size image

1 with osmium tetraoxide proceeded with extremed high diastereoselectivity to give only methyl

Full-size image

2. Configurations of the new stereogenic centers (C-2,3) in 2 were determined by degradation of the C-5,6,7,8 fragment to the well-known methyl

Full-size image

7. Transformation of 2 into the required

Full-size image

10, was achieved by a methodology that implied, protection to 8, reduction of the ester group in 8 to a hydroxymethyl group in 9, and finally deprotection to the free

Full-size image

10. On the other hand, epoxidation reaction on

Full-size image

11 afforded only the corresponding 2,3-anhydro derivative 12 with configuration, as could be demonstrated by degradation to (S)-1,2,4-trimetoxybutane 16, which synthesis is reported herein.     

Pseudo-holomorphic maps and bubble trees

This paper proves a strong convergence theorem for sequences of pseudo-holomorphic maps from a Riemann surface to a symplectic manifoldN with tamed almost complex structure. (These are the objects used by Gromov to define his symplectic invariants.) The paper begins by developing some analytic facts about such maps, including a simple new isoperimetric inequality and a new removable singularity theorem. The main technique is a general procedure for renormalizing sequences of maps to obtain “bubbles on bubbles.” This is a significant step beyond the standard renormalization procedure of Sacks and Uhlenbeck. The renormalized maps give rise to a sequence of maps from a “bubble tree”—a map from a wedge Σ V S² V S² V ... →N. The main result is that the images of these renormalized maps converge in L^1,2 ∪C° to the image of a limiting pseudo-holomorphic map from the bubble tree. This implies several important properties of the bubble tree. In particular, the images of consecutive bubbles in the bubble tree intersect, and if a sequence of maps represents a homology class then the limiting map represents this class.     

Biomimetic syntheses of syncarpurea

Simple syntheses of syncarpurea (1) from syncarpic acid and the amino acids ornithine or citrulline are presented.     

A selective gas chromatographic detector for polynuclear aromatics based on ultraviolet fluorescence

A vapor-phase fluorescence detector for the analysis of mixtures of polynuclear aromatic ring systems has been developed. This system utilizes wide bandpass excitation and wide band emission filters, thus increasing sensitivity and decreasing the complexity of previously designed instruments. The sensitivity of the detector has been demonstrated to be at the nanogram level with reasonable precision.     

Studies of the oxovanadium-organophosphonate system: Hydrothermal synthesis and crystal structure of the mixed valence cluster [V5O9(PhPO3)3(PhPO3H)2]2− and a comparison to the structure of the fully oxidized parent cluster [V5O7(OCH3)2(PhPO3)5]1−

The room temperature reaction of (Bu₄N)₃V₅O₁₄ with PhPO₃H₂ in methanol yields the pentanuclear V(V) cluster (Bu₄N)[V₅O₇(OCH₃)₂(PhPO₃)₅]·CH₃OH (1·CH₃OH). In contrast, the hydrothermal reaction of (Ph₄P) [VO₂Cl₂], PhPO₃H₂ and (NH₄)H₂PO₄ at 125°C for 96 hr yields the mixed valence V(IV)/V(V) species (Ph₄P)₂[V₅O₉(PhPO₃)₃(PhPO₃H)₂] (3). While the anions of both 1 and 3 exhibit a pentanuclear core, the structural consequences of 1-electron reduction of the fully oxidized cluster of 1 to produce 3 are quite dramatic, including reduction in coordination numbers at two vanadium sites and protonation of two phosphonate oxygen sites with concomitant structural reorganization. Crystal data: 1, monoclinic P2₁/n,a=12.167(2) Å,b=23.348(5) Å,c=22.508(5) Å,β=98.49(2)°,V=6323.9(19) ų,Z=4,D _calc=1.558 g cm^?3; 3, triclinic, $P\bar 1$ ,a=13.478(3) Å,b=14.399(3) Å,c=23.638(5) Å,α=72.53(2)°,β=85.58(2)°,γ=69.88(4)°,V=4107.0(16) ų,Z=2, D_calc=1.479 g cm^?3.     

Gilmicolin and Mycorrhizinol,Two New Metabolites of Gilmaniella humicolaBARRON

The structure of gilmicolin and mycorrhizinol, two new metabolites isolated from culture filtrates of Gilmaniella humicola BARRON , have been shown to be 3 and 15 respectively by spectral and chemical studies. The X-ray analysis of gilmicolin ( 3 ) is also reported.