- Asymmetric Synthesis of Vitamin D3 Analogues: Organocatalytic Desymmetrization Approach toward the A-Ring Precursor of Calcifediol
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A novel asymmetric synthesis has been developed for the construction of the A-ring of a chiral precursor to calcifediol. The highlights of this synthesis include (i) the introduction of the stereochemistry at the C5-position of the A-ring through the orga
- Wang, Haifeng,Yan, Linjie,Wu, Yan,Lu, Yipei,Chen, Fener
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p. 5452 - 5455
(2015/11/18)
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- Total synthesis of biologically active 20S-hydroxyvitamin D3
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A total synthetic strategy of 20S-hydroxyVitamin D3 [20S-(OH)D3] involving modified synthesis of key intermediates 7 and 12, Grignard reaction to stereoselectively generate 20S-OH and Wittig-Horner coupling to establish D3 framework, was completed in 16 steps with an overall yield of 0.4%. The synthetic 20S-(OH)D3 activated Vitamin D receptor (VDR) and initiated the expression of downstream genes. In addition, 20S-(OH)D3 showed similar inhibitory potency as calcitriol [1,25(OH)2D3] on proliferation of melanoma cells.
- Wang, Qinghui,Lin, Zongtao,Kim, Tae-Kang,Slominski, Andrzej T.,Miller, Duane D.,Li, Wei
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p. 153 - 162
(2015/12/01)
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- Furan approach to vitamin D analogues. Synthesis of the A-ring of calcitriol and 1α-hydroxy-3-deoxyvitamin D3
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The A-rings of calcitriol (1α,25-dihydroxyvitamin D3) and 1α-hydroxy-3-deoxyvitamin D3 were synthesized using the furan approach. The critical steps in the synthesis of the A-ring of calcitriol involved an asymmetric carbonyl-ene reaction of 3-methylene-2,3-dihydrofuran with 3-(tert-butyldimethylsiloxy)propanal, a diastereoselective Friedel-Crafts hydroxyalkylation, an oxidation of the 2,3-disubstituted furan to give a γ-hydroxybutenolide, and a Peterson olefination. The A-ring (Z)-dienol of calcitriol was synthesized in 12 steps from 3-(tert-butyldimethylsiloxy)propanal in 17% yield.
- Miles, William H.,Connell, Katelyn B.,Ulas, Goezde,Tuson, Hannah H.,Dethoff, Elizabeth A.,Mehta, Varun,Thrall, April J.
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supporting information; experimental part
p. 6820 - 6829
(2010/12/18)
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- NOVEL METHOD
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There is provided a method of prevention of adhesions, eg surgical adhesions, which comprises using a vitamin D compound.
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- SYNTHESIS OF 1α-FLUORO-25-HYDROXY-16-23E-DIENE-26,27-BISHOMO-20-EPI-CHOLECALCIFEROL
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The invention provides a method of producing 20-methyl vitamin D3 compounds of formula (I). The method includes hydroxylation, carbonyl reduction, fluoride substitution, epoxide deoxygenation, and Wittig-type couplings.
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Page/Page column 13; 38-39
(2008/12/07)
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- NOVEL METHOD
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The invention provides for the use of Vitamin D compounds such as 1-alpha-fluoro-25- hydroxy-16,23E-diene-26,27-bishomo-20-epi-cholecalciferol, in the prevention or treatment of prostate cancer.
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- SYNTHESIS OF 1α-FLUORO-25-HYDROXY-16-23E-DIENE-26,27-BISHOMO-20-EPI-CHOLECALCIFEROL
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The invention provides a method of producing 20-methyl vitamin D3 compounds of formula (I). The method includes allylic and olefin oxidation, decarbonylation, carbonyl reduction, fluoride substitution, epoxide deoxygenation, and Wittig-type couplings.
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Page/Page column 48
(2008/06/13)
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- Preparation of an A-ring building block for the total synthesis of 1α,25-dihydroxy vitamin D3 and structurally related congeners: Lipase-catalyzed stereoselective esterification of a suitable epoxyalcohol
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An useful A-ring building block for the total synthesis of vitamin D3 congeners, compound 7, has been prepared starting from vitamin D2 by a chemo-enzymatic approach that relies on lipase-catalyzed acylation in an organic solvent for the stereoselective step. Copyright (C) 2000 Elsevier Science Ltd.
- Ferraboschi, Patrizia,Reza-Elahi, Shahrzad,Scotti, Luca,Santaniello, Enzo
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p. 2665 - 2668
(2007/10/03)
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- The modified Julia olefination in vitamin D2 synthesis
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A partial synthesis of vitamin D2 employing fragments derived from a new improved degradation procedure is described. The 7,8-double bond of the vitamin D triene system was synthesised via the modified Julia olefination. The new procedure is more efficient than the classical Julia olefination.
- Blakemore,Kocienski,Marzcak,Wicha
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p. 1209 - 1215
(2007/10/03)
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- On the Julia Alkenylation reaction in vitamin D synthesis. Isolation of four geometrical isomers of vitamin D4
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Coupling of sulfone 2 and aldehyde 3b using the Julia alkenylation procedure has been reexamined using modern product separation techniques. It was found that vitamin D4 1b and its geometric isomers 10, 11 and 12 are formed in a ratio of 75:10:10:5, respectively. The building blocks 2 and 3b were prepared from vitamin D2. Correlations for the structure assignment of vitamin D stereoisomers by 1H NMR spectroscopy are presented.
- Blakmore,Grzywacz,Kocienski,Marczak,Wicha
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p. 1209 - 1217
(2007/10/03)
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- Synthesis of Retiferol RAD1 and RAD2, the Lead Representatives of a New Class of des-CD Analogs of Cholecalciferol
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The design and total convergent synthesis are described for the leading representatives of the new class of analogs of cholecalciferol with the CD-ring system replaced with a two-carbon aliphatic spacer.The leading representatives of C21 retiferols (RAD1
- Kutner, A.,Zhao, H.,Fitak, H.,Wilson, S. R.
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- Convergent Approaches to the Vitamin D Skeleton Using a Transition Metal Catalyzed Carbometalation/Capture Strategy
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Two concise, highly convergent strategies for the synthesis of Vitamin D derivatives are presented .Beginning with synthons of exceedingly low complexity, each approach utilizes a transition metal catalyzed intramolecular carbometalation for the stereosel
- Nuss, John M.,Murphy, Martin M.,Rennels, Roger A.,Heravi, Magid H.,Mohr, Brent J.
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p. 3079 - 3082
(2007/10/02)
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- Studies on a Convergent Route to Side-Chain Analogues of Vitamin D: 25-Hydroxy-23-oxavitamin D3
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Permanganate oxidation of vitamin D3 affords the 7,8-diol 4a, which was successively silylated to 4b and then oxidatively cleaved and reduced to afford 3c.The latter was converted in several steps to phosphine oxide 3b, a useful A-ring fragment for analog
- Toh, H. T.,Okamura, William H.
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p. 1414 - 1417
(2007/10/02)
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