A Novel Synthesis of 19-Nor 1α,25-dihydroxyvitamin D3 and Related Analogues

Huang, Pei‐Qiang; Sabbe, K.; Pottie, M.; Vandewalle, M.

doi:10.1016/0040-4039(95)01730-6

Cited by 33 publications

(20 citation statements)

References 14 publications

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“…We have already reported in preliminary form the synthesis of the 19-nor vitamin D 3 analogues 1b and 2 by this cyclovitamin strategy. [17] Here we report a practical synthesis of the bicyclo[3.1.0]-cyclohexane precursor 14, applicable to large-scale production. Our previously described syntheses, starting from 22, [17a] 23, [17b] or 24 (Figure 2), [17c] showed several drawbacks relating to scaling up or purification.…”

Section: Introductionmentioning

confidence: 99%

A Practical Synthesis of 14-epi-19-nor-1α,25-Dihydroxyvitamin D3 Analogues and Their A-ring Epimers

Zhao

Tian

et al. 2001

Eur. J. Org. Chem.

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Section: Introductionmentioning

confidence: 99%

A Practical Synthesis of 14-epi-19-nor-1α,25-Dihydroxyvitamin D3 Analogues and Their A-ring Epimers

Zhao

Tian

et al. 2001

Eur. J. Org. Chem.

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“…It is noteworthy that clean S N 2 reactions using tosylates (4 R )- 3 and (4 S )- 3 proceeded smoothly to produce four key cyclopropane carbonitrile nitrile precursors, (1 R ,2 S )- 4 , (1 S ,2 S )- 4 , (1 S ,2 R )- 4 , and (1 R ,2 R )- 4 , with excellent optical purities (all 98% ee, as determined by HPLC analysis). Related chirality-induced cyclopropane-forming reactions have been addressed in previous reports, namely a representative review [18], syntheses of liquid crystals [16], and syntheses of dihydroxy vitamin D 3 analogues [19], petrosterol [20], chiral cyclobutanes [21], bicifadin [22], norchrysanthemic acid [23], and grandisol [23].…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Stereostructure-Activity Relationship of Novel Pyrethroids Possessing Two Asymmetric Centers on a Cyclopropane Ring

et al. 2019

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2-Methylcyclopropane pyrethroid insecticides bearing chiral cyanohydrin esters or chiral ethers and two asymmetric centers on the cyclopropane ring, were synthesized. These compounds were designed using a “reverse connection approach” between the isopropyl group in Fenvalerate, and between two dimethyl groups in an Etofenprox analogue (the methyl, ethyl form), respectively. These syntheses were achieved by accessible ring opening reactions of commercially available (±)-, (R)-, and (S)-propylene oxides using 4-chlorobenzyl cyanide anion as the crucial step, giving good overall yield of the product with >98% ee. The insecticidal activity against the common mosquito (Culex pipiens pallens) was assessed for pairs of achiral diastereomeric (1R*,2S*)-, (1R*,2R*)-cyanohydrin esters, and (1R*,2S*)-, (1R*,2R*)-ethers; only the (1R*,2R*)-ether was significantly effective. For the enantiomeric (1S,2S)-ether and (1R,2R)-ether, the activity was clearly centered on the (1R,2R)-ether. The present stereostructure‒activity relationship revealed that (i) cyanohydrin esters derived from fenvalerate were unexpectedly inactive, whereas ethers derived from etofenprox were active, and (ii) apparent chiral discrimination between the (1S,2S)-ether and the (1R,2R)-ether was observed. During the present synthetic study, we performed alternative convergent syntheses of Etofenprox and novel 4-EtO-type (1S,2S)- and (1R,2R)-pyrethroids from the corresponding parent 4-Cl-type pyrethroids, by utilizing a recently-developed hydroxylation cross-coupling reaction.

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“…[35] The same conditions were applied to the ligation of antigen 20, lysinyl core 17, and 2-thioethyl a-d-galactopyranoside 26 [23] and the thio derivative of d-(À)-quinic acid 29. The latter compound was obtained in 71 % yield from quinide 27, [36] which was treated with cysteamine in degassed H 2 O. Compound 29 was purified and stored as its disulfide derivative 28, and reduced prior to use (Scheme 4).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of Clustered Glycoside-Antigen Conjugates by Two One-Pot, Orthogonal, Chemoselective Ligation Reactions: Scope and Limitations

2001

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Major histocompatibility class II antigens have been bound to clustered glycosides for selective targeting of the dendritic cell mannose receptor. Di-, tetra-, and octavalent glycoside-antigen conjugates have been obtained after two, orthogonal, hydrazone/thioether ligations, performed by using thio derivatives of D-mannose, D-galactose, or D(-)-quinic acid, glyoxylyl (or hydrazino)-N-chloroacetylated lysinyl trees, and N-terminal hydrazino (or glyoxylyl) peptide antigens. Successful one-pot condensations have been developed to account for the nature of the antigens and the valency of the trees.

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A Novel Synthesis of 19-Nor 1α,25-dihydroxyvitamin D3 and Related Analogues

Cited by 33 publications

References 14 publications

A Practical Synthesis of 14-epi-19-nor-1α,25-Dihydroxyvitamin D3 Analogues and Their A-ring Epimers

A Practical Synthesis of 14-epi-19-nor-1α,25-Dihydroxyvitamin D3 Analogues and Their A-ring Epimers

Synthesis and Stereostructure-Activity Relationship of Novel Pyrethroids Possessing Two Asymmetric Centers on a Cyclopropane Ring

Synthesis of Clustered Glycoside-Antigen Conjugates by Two One-Pot, Orthogonal, Chemoselective Ligation Reactions: Scope and Limitations

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