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[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. 相似文献
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Marcus J. Curtis‐Long Yimon Aye Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(22):5402-5416
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.
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Aye Aye Mar Ali Koohang Nathan D. Majewski Erika L. Szotek David A. Eiznhamer Michael T. Flavin Ze Qi Xu 《中国化学快报》2009,20(10):1141-1144
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. 相似文献
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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. 相似文献
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Aye Aye Mar Ali Koohang Nathan D.Majewski Erika L.Szotek David A.Eiznhamer Michael T.Flavin 《中国化学快报》2009,(10)
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... 相似文献
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Albert Khilevich John D. Rizzo Michael T. Flavin Abram K. Sheinkman Aye Mar Alla Kucherenko 《合成通讯》2013,43(20):3757-3771
Combined aldol/Mitsunobu reactions have been employed for the first time for synthesis of 2,3-dimethyl chroman-4-ones, intermediates for calanolide anti-HIV agents. Thus, the lithium enolate of chromene 1 reacted with acetaldehyde at -78°C to afford the aldol products 4 and 5. Under Mitsunobu conditions (Ph3P/DEAD), the syn aldol product 4 led to the formation of trans-2,3-dimethyl chroman-4-one 2 while the anti aldol product 5 yielded both trans and cis derivatives (2 and 3). The use of other phosphorous and azo compounds in this reaction has also been investigated. 相似文献