Asymmetric, anti-selective scandium-catalyzed Sakurai additions to glyoxyamide. Applications to the syntheses of N-boc D-alloisoleucine and D-isoleucine

[reaction: see text] An enantio- and diastereoselective Sakurai-Hosomi reaction, catalyzed by chiral scandium pyridyl-bis(oxazoline) (pybox) complexes, has been developed. Both alkyl- and aryl-substituted allylsilanes are effective coupling partners with N-phenylglyoxamide. Applications of this reaction to the asymmetric syntheses of N-Boc D-alloisoleucine and D-isoleucine are described.     

Vinyl‐, Propargyl‐, and Allenylsilicon Reagents in Asymmetric Synthesis: A Relatively Untapped Resource of Environmentally Benign Reagents

Green carbanion surrogates : Organotrialkylsilanes occupy a niche in the array of ‘green’ carbon nucleophiles open to chemists that few other reagents can fill. Despite being known for over 30 years, it is only recently that their true worth in stereoselective carbonyl addition and related processes has started to emerge, primarily due to their low reactivity. It is our hope that this minireview will make the true worth of these reagents more widely known, setting the stage for expanded usage of these versatile yet benign reagents in organic synthesis.

     

Synthesis and cytotoxicity of 28-carboxymethoxy lupane triterpenoids. Preference of 28-O-acylation over 28-O-alkylation of betulin by ethyl bromoacetate

28-Carboxymethoxy lupane tritepenoids 3 and 4 were synthesized by alkylation of betulin with the THP protected 2-hydroxyethyl iodide followed by oxidation and reduction.Direct reaction of betulin (5) or betulone (10) with ethyl bromoacetate led to 28-O-acylation, instead of 28-O-alkylation.The targeted compounds 3 and 4 were not cytotoxic at the highest concentrationtested (75 mmol/L), suggesting that elongation of the chain length at the 28-position in both betulinic acid (1) and betulonic acid (2)was detrimental to the cytotoxicity.The acylation products 28-O-bromoacetates (8a, 8b and 11) and 28-O-methoxyacetate 13exhibited cytotoxicity against several cancer cell lines tested.     

Synthesis and cytotoxicity of 28-carboxymethoxy lupane triterpenoids.Preference of 28-O-acylation over 28-O-alkylation of betulm by ethyl bromoacetate

28-Carboxymethoxy lupane tritepenoids 3 and 4 were synthesized by alkylation of betulin with the THP protected 2- hydroxyethyl iodide followed by oxidation and reduction.Direct reaction of betulin(5) or betulone(10) with ethyl bromoacetate led to 28-O-acylation,instead of 28-O-alkylation.The targeted compounds 3 and 4 were not cytotoxic at the highest concentration tested(75μmol/L),suggesting that elongation of the chain length at the 28-position in both betulinic acid(1) and betulonic acid(2) was detrim...     

Theoretical Investigation into Production of Double-Λ Hypernuclei from Stopped Ξ − on 6Li

We have investigated theoretically a feasible nuclear reaction to produce light double-Λ hypernuclei by choosing a suitable target. In the reaction from stopped Ξ ^? on ⁶Li target light doubly-strange nuclei, ${^5_{\Lambda\Lambda}{\rm H}}$ and ${^6_{\Lambda\Lambda}{\rm He}}$ , are produced: we have calculated the formation ratio of ${^5_{\Lambda\Lambda}{\rm H}}$ to ${^6_{\Lambda\Lambda}{\rm He}}$ for Ξ ^? absorptions from 2S, 2P and 3D orbitals of Ξ ^?–⁶Li atom by assuming a d?α cluster model for ⁶Li. From this cluster model the d?α relative wave functions has a node due to Pauli exclusion among nucleons belonging to d and α clusters. Two kinds of d?α wave functions, namely 1s relative wave function with a phenomenological one-range Gaussian (ORG) potential and that of an orthogonality-condition model (OCM) are used. It is found that the probability of ${^5_{\Lambda\Lambda}{\rm H}}$ formation is larger than that of ${^6_{\Lambda\Lambda}{\rm He}}$ for all absorption orbitals: in the case of the major 3D absorption their ratio is 1.08 for ORG and 1.96 for OCM. The dominant low momentum component of the d?α relative wave function favors the ${^5_{\Lambda\Lambda}{\rm H}}$ formation with a low Q value compared to the ${^6_{\Lambda\Lambda}{\rm He}}$ formation with a high Q value. We have also calculated momentum distributions of emitted particles, d and n, displaying continuum spectra for single-Λ hypernuclei, ${^4_{\Lambda}{\rm H}}$ and ${^5_{\Lambda}{\rm He}}$ , and line spectra for the ${^5_{\Lambda\Lambda}{\rm H}}$ and ${^6_{\Lambda\Lambda}{\rm He}}$ nuclei. Thus, our present theoretical analysis would be a significant contribution to experiments in the strangeness ?2 sector of hypernuclear physics.     

On-column N-dearylation of 2-azetidinones by silica-supported ceric ammonium nitrate

A modified traditional preparative chromatographic column can be used to achieve quantitative N-dearylation of N-(alkoxyphenyl), N-(alkoxynaphthyl), and N-(alkoxybenzyl)-2-azetidinones under mild conditions. Starting materials are charged on top of the column and the pure N-unsubstituted 2-azetidinones leave the column minutes later without need for other purifications. The yields are good-to-excellent and the reaction condition is mild, easy, efficient, and cheap.