IL93454A - Preparation of Chiral Alkyl Aryl Sulfon History Used as Starting Materials for Side Chain Steroids - Google Patents

Preparation of Chiral Alkyl Aryl Sulfon History Used as Starting Materials for Side Chain Steroids

Info

Publication number: IL93454A
Authority: IL; Israel
Prior art keywords: group; hydroxy; chiral; protected; chiral center
Prior art date: 1989-03-09

Application number

IL9345490A

Other languages

English (en)

Hebrew (he)

Other versions

IL93454A0 (en

Original Assignee

Wisconsin Alumni Res Found

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1989-03-09

Filing date

1990-02-20

Publication date

1994-10-07

1990-02-20 Application filed by Wisconsin Alumni Res Found filed Critical Wisconsin Alumni Res Found

1990-11-29 Publication of IL93454A0 publication Critical patent/IL93454A0/xx

1994-10-07 Publication of IL93454A publication Critical patent/IL93454A/en

Links

238000002360 preparation method Methods 0.000 title claims abstract description 10
239000002243 precursor Substances 0.000 title description 3
125000002877 alkyl aryl group Chemical group 0.000 title description 2
125000002345 steroid group Chemical group 0.000 title 1
238000000034 method Methods 0.000 claims abstract description 48
-1 vitamin D compounds Chemical class 0.000 claims abstract description 27
150000003457 sulfones Chemical class 0.000 claims abstract description 15
125000000217 alkyl group Chemical group 0.000 claims abstract description 10
229910052717 sulfur Inorganic materials 0.000 claims description 16
239000000203 mixture Substances 0.000 claims description 14
150000003462 sulfoxides Chemical class 0.000 claims description 11
NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
239000011593 sulfur Substances 0.000 claims description 9
150000002148 esters Chemical class 0.000 claims description 7
125000003118 aryl group Chemical group 0.000 claims description 6
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
150000004795 grignard reagents Chemical class 0.000 claims description 4
229910052739 hydrogen Inorganic materials 0.000 claims description 4
239000001257 hydrogen Substances 0.000 claims description 4
125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 claims description 4
239000007818 Grignard reagent Substances 0.000 claims description 3
125000004434 sulfur atom Chemical group 0.000 claims description 3
239000003153 chemical reaction reagent Substances 0.000 claims description 2
125000000753 cycloalkyl group Chemical group 0.000 claims description 2
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
125000005843 halogen group Chemical group 0.000 claims description 2
125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
150000002431 hydrogen Chemical class 0.000 claims 3
125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 claims 1
125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 claims 1
229910052736 halogen Inorganic materials 0.000 claims 1
125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
YXFVVABEGXRONW-UHFFFAOYSA-N toluene Substances CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 1
150000003431 steroids Chemical class 0.000 abstract description 21
229930003316 Vitamin D Natural products 0.000 abstract description 18
QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 abstract description 18
235000019166 vitamin D Nutrition 0.000 abstract description 18
239000011710 vitamin D Substances 0.000 abstract description 18
229940046008 vitamin d Drugs 0.000 abstract description 18
OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 16
229910052799 carbon Inorganic materials 0.000 abstract description 16
230000015572 biosynthetic process Effects 0.000 abstract description 8
238000003786 synthesis reaction Methods 0.000 abstract description 6
230000000707 stereoselective effect Effects 0.000 abstract 1
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
150000001875 compounds Chemical class 0.000 description 15
150000003710 vitamin D derivatives Chemical class 0.000 description 15
238000006243 chemical reaction Methods 0.000 description 8
239000000047 product Substances 0.000 description 8
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
238000010276 construction Methods 0.000 description 7
229940093499 ethyl acetate Drugs 0.000 description 7
235000019439 ethyl acetate Nutrition 0.000 description 7
XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
239000000243 solution Substances 0.000 description 6
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
238000009833 condensation Methods 0.000 description 5
230000005494 condensation Effects 0.000 description 5
230000000875 corresponding effect Effects 0.000 description 5
DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical class [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 5
229940088594 vitamin Drugs 0.000 description 5
239000011782 vitamin Substances 0.000 description 5
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
238000003747 Grignard reaction Methods 0.000 description 4
125000002252 acyl group Chemical group 0.000 description 4
239000012074 organic phase Substances 0.000 description 4
238000000926 separation method Methods 0.000 description 4
150000003722 vitamin derivatives Chemical class 0.000 description 4
YKZYRVIFGPGJJI-PWGHIRGTSA-N 1-[(1s,2r)-1-[(1s,2r)-2,3-dimethyl-1-(4-methylphenyl)butyl]sulfinyl-2,3-dimethylbutyl]-4-methylbenzene Chemical compound C1([C@H]([C@H](C)C(C)C)S(=O)[C@@H]([C@H](C)C(C)C)C=2C=CC(C)=CC=2)=CC=C(C)C=C1 YKZYRVIFGPGJJI-PWGHIRGTSA-N 0.000 description 3
MZWRKRWZTKMJOZ-FGZHOGPDSA-N 2-[(2r)-2,3-dimethylbutyl]-4-[3-[(2r)-2,3-dimethylbutyl]-4-methylphenyl]sulfonyl-1-methylbenzene Chemical compound C1=C(C)C(C[C@@H](C)C(C)C)=CC(S(=O)(=O)C=2C=C(C[C@@H](C)C(C)C)C(C)=CC=2)=C1 MZWRKRWZTKMJOZ-FGZHOGPDSA-N 0.000 description 3
MZWRKRWZTKMJOZ-VXKWHMMOSA-N 2-[(2s)-2,3-dimethylbutyl]-4-[3-[(2s)-2,3-dimethylbutyl]-4-methylphenyl]sulfonyl-1-methylbenzene Chemical compound C1=C(C)C(C[C@H](C)C(C)C)=CC(S(=O)(=O)C=2C=C(C[C@H](C)C(C)C)C(C)=CC=2)=C1 MZWRKRWZTKMJOZ-VXKWHMMOSA-N 0.000 description 3
WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
125000004183 alkoxy alkyl group Chemical group 0.000 description 3
229910052786 argon Inorganic materials 0.000 description 3
UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
238000004128 high performance liquid chromatography Methods 0.000 description 3
239000000543 intermediate Substances 0.000 description 3
239000002207 metabolite Substances 0.000 description 3
229920006395 saturated elastomer Polymers 0.000 description 3
239000000741 silica gel Substances 0.000 description 3
229910002027 silica gel Inorganic materials 0.000 description 3
239000002904 solvent Substances 0.000 description 3
229930003231 vitamin Natural products 0.000 description 3
235000013343 vitamin Nutrition 0.000 description 3
FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
239000012267 brine Substances 0.000 description 2
230000008878 coupling Effects 0.000 description 2
238000010168 coupling process Methods 0.000 description 2
238000005859 coupling reaction Methods 0.000 description 2
230000000694 effects Effects 0.000 description 2
OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 2
238000003818 flash chromatography Methods 0.000 description 2
125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 2
150000002430 hydrocarbons Chemical group 0.000 description 2
239000012299 nitrogen atmosphere Substances 0.000 description 2
239000000376 reactant Substances 0.000 description 2
239000011541 reaction mixture Substances 0.000 description 2
GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
238000003756 stirring Methods 0.000 description 2
239000000126 substance Substances 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
QOWCBCXATJITSI-ZLNGONTQSA-N (6r)-6-[(1r,3as,4e,7ar)-4-[(2z)-2-[(5s)-5-hydroxy-2-methylidenecyclohexylidene]ethylidene]-7a-methyl-2,3,3a,5,6,7-hexahydro-1h-inden-1-yl]-2-methylheptane-1,2-diol Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@@H](CCCC(C)(O)CO)C)=C\C=C1\C[C@@H](O)CCC1=C QOWCBCXATJITSI-ZLNGONTQSA-N 0.000 description 1
YKZYRVIFGPGJJI-JPMIEVGJSA-N 1-[(1s,2s)-1-[(1s,2s)-2,3-dimethyl-1-(4-methylphenyl)butyl]sulfinyl-2,3-dimethylbutyl]-4-methylbenzene Chemical compound C1([C@H]([C@@H](C)C(C)C)S(=O)[C@@H]([C@@H](C)C(C)C)C=2C=CC(C)=CC=2)=CC=C(C)C=C1 YKZYRVIFGPGJJI-JPMIEVGJSA-N 0.000 description 1
MPHUAKIJAGYUEQ-FGZHOGPDSA-N 2-[(2r)-2,3-dimethylbutyl]-4-[3-[(2r)-2,3-dimethylbutyl]-4-methylphenyl]sulfinyl-1-methylbenzene Chemical compound C1=C(C)C(C[C@@H](C)C(C)C)=CC(S(=O)C=2C=C(C[C@@H](C)C(C)C)C(C)=CC=2)=C1 MPHUAKIJAGYUEQ-FGZHOGPDSA-N 0.000 description 1
NHQDETIJWKXCTC-UHFFFAOYSA-N 3-chloroperbenzoic acid Chemical compound OOC(=O)C1=CC=CC(Cl)=C1 NHQDETIJWKXCTC-UHFFFAOYSA-N 0.000 description 1
HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
239000004215 Carbon black (E152) Substances 0.000 description 1
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical class OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
239000002253 acid Substances 0.000 description 1
150000001298 alcohols Chemical class 0.000 description 1
150000001336 alkenes Chemical group 0.000 description 1
150000001350 alkyl halides Chemical class 0.000 description 1
125000005103 alkyl silyl group Chemical group 0.000 description 1
239000008346 aqueous phase Substances 0.000 description 1
150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
125000004391 aryl sulfonyl group Chemical group 0.000 description 1
208000027697 autoimmune lymphoproliferative syndrome due to CTLA4 haploinsuffiency Diseases 0.000 description 1
125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
230000004071 biological effect Effects 0.000 description 1
239000006227 byproduct Substances 0.000 description 1
239000012230 colorless oil Substances 0.000 description 1
238000001816 cooling Methods 0.000 description 1
230000002596 correlated effect Effects 0.000 description 1
239000013078 crystal Substances 0.000 description 1
229940043279 diisopropylamine Drugs 0.000 description 1
238000006073 displacement reaction Methods 0.000 description 1
125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
238000002474 experimental method Methods 0.000 description 1
239000000284 extract Substances 0.000 description 1
150000004820 halides Chemical class 0.000 description 1
125000000623 heterocyclic group Chemical group 0.000 description 1
229930195733 hydrocarbon Natural products 0.000 description 1
125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
238000011065 in-situ storage Methods 0.000 description 1
239000010410 layer Substances 0.000 description 1
239000011777 magnesium Substances 0.000 description 1
229910052749 magnesium Inorganic materials 0.000 description 1
238000004519 manufacturing process Methods 0.000 description 1
MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
APVPOHHVBBYQAV-UHFFFAOYSA-N n-(4-aminophenyl)sulfonyloctadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NS(=O)(=O)C1=CC=C(N)C=C1 APVPOHHVBBYQAV-UHFFFAOYSA-N 0.000 description 1
125000001624 naphthyl group Chemical group 0.000 description 1
125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
230000003287 optical effect Effects 0.000 description 1
239000012044 organic layer Substances 0.000 description 1
150000004967 organic peroxy acids Chemical class 0.000 description 1
239000003960 organic solvent Substances 0.000 description 1
230000003647 oxidation Effects 0.000 description 1
238000007254 oxidation reaction Methods 0.000 description 1
150000004965 peroxy acids Chemical class 0.000 description 1
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
235000002378 plant sterols Nutrition 0.000 description 1
125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
238000000746 purification Methods 0.000 description 1
238000009877 rendering Methods 0.000 description 1
238000004007 reversed phase HPLC Methods 0.000 description 1
239000012047 saturated solution Substances 0.000 description 1
229910001023 sodium amalgam Inorganic materials 0.000 description 1
229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
235000017557 sodium bicarbonate Nutrition 0.000 description 1
235000010265 sodium sulphite Nutrition 0.000 description 1
239000011343 solid material Substances 0.000 description 1
238000004611 spectroscopical analysis Methods 0.000 description 1
238000010561 standard procedure Methods 0.000 description 1
125000001424 substituent group Chemical group 0.000 description 1
125000000547 substituted alkyl group Chemical group 0.000 description 1
125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
125000003944 tolyl group Chemical group 0.000 description 1
230000009466 transformation Effects 0.000 description 1
125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
238000002424 x-ray crystallography Methods 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/14—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Steroid Compounds (AREA)
Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

IL9345490A 1989-03-09 1990-02-20 Preparation of Chiral Alkyl Aryl Sulfon History Used as Starting Materials for Side Chain Steroids IL93454A (en)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
US32141689A	1989-03-09	1989-03-09

Publications (2)

Publication Number	Publication Date
IL93454A0 IL93454A0 (en)	1990-11-29
IL93454A true IL93454A (en)	1994-10-07

Family

ID=23250531

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
IL9345490A IL93454A (en)	1989-03-09	1990-02-20	Preparation of Chiral Alkyl Aryl Sulfon History Used as Starting Materials for Side Chain Steroids

Country Status (14)

Country	Link
US (1)	US5089647A (de)
EP (1)	EP0386794B1 (de)
JP (1)	JP2562999B2 (de)
KR (1)	KR0174524B1 (de)
CN (1)	CN1029398C (de)
AT (1)	ATE85045T1 (de)
AU (1)	AU631405B2 (de)
CA (1)	CA1339383C (de)
DE (1)	DE69000808T2 (de)
DK (1)	DK0386794T3 (de)
ES (1)	ES2054126T3 (de)
IL (1)	IL93454A (de)
NZ (1)	NZ232733A (de)
WO (1)	WO1990010618A1 (de)

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US4927815A (en) *	1988-04-29	1990-05-22	Wisconsin Alumni Research Foundation	Compounds effective in inducing cell differentiation and process for preparing same

1989
- 1989-09-22 CA CA000612520A patent/CA1339383C/en not_active Expired - Lifetime
1990
- 1990-02-16 JP JP2504067A patent/JP2562999B2/ja not_active Expired - Lifetime
- 1990-02-16 KR KR1019900702410A patent/KR0174524B1/ko not_active Expired - Lifetime
- 1990-02-16 AU AU51672/90A patent/AU631405B2/en not_active Expired
- 1990-02-16 WO PCT/US1990/000953 patent/WO1990010618A1/en not_active Ceased
- 1990-02-20 IL IL9345490A patent/IL93454A/en not_active IP Right Cessation
- 1990-02-28 NZ NZ232733A patent/NZ232733A/en unknown
- 1990-03-09 ES ES90104565T patent/ES2054126T3/es not_active Expired - Lifetime
- 1990-03-09 DK DK90104565.8T patent/DK0386794T3/da active
- 1990-03-09 CN CN90101778A patent/CN1029398C/zh not_active Expired - Lifetime
- 1990-03-09 AT AT90104565T patent/ATE85045T1/de not_active IP Right Cessation
- 1990-03-09 DE DE9090104565T patent/DE69000808T2/de not_active Expired - Lifetime
- 1990-03-09 EP EP90104565A patent/EP0386794B1/de not_active Expired - Lifetime
- 1990-04-11 US US07/507,971 patent/US5089647A/en not_active Expired - Lifetime

Also Published As

Publication number	Publication date
AU631405B2 (en)	1992-11-26
DK0386794T3 (da)	1993-03-22
NZ232733A (en)	1992-07-28
AU5167290A (en)	1990-10-09
EP0386794A1 (de)	1990-09-12
US5089647A (en)	1992-02-18
WO1990010618A1 (en)	1990-09-20
KR920700196A (ko)	1992-02-19
CN1048849A (zh)	1991-01-30
ATE85045T1 (de)	1993-02-15
IL93454A0 (en)	1990-11-29
KR0174524B1 (ko)	1999-04-01
CA1339383C (en)	1997-08-26
DE69000808D1 (de)	1993-03-11
CN1029398C (zh)	1995-08-02
JP2562999B2 (ja)	1996-12-11
JPH03504862A (ja)	1991-10-24
EP0386794B1 (de)	1993-01-27
ES2054126T3 (es)	1994-08-01
DE69000808T2 (de)	1993-05-19

Legal Events

Date	Code	Title
1996-05-14	KB	Patent renewed
2000-08-13	KB	Patent renewed
2004-03-28	KB	Patent renewed
2008-03-23	KB	Patent renewed
2010-12-30	EXP	Patent expired

Publication	Publication Date	Title
US4973584A (en)	1990-11-27	Novel 1α-hydroxyvitamin D2 epimer and derivatives
Nicolaou	1981	Organoselenium-induced cyclizations in organic synthesis
US4338250A (en)	1982-07-06	1-Hydroxylation process
JP3494637B2 (ja)	2004-02-09	１９−ノル−ビタミンｄ化合物の中間体の製造方法
US4847012A (en)	1989-07-11	Vitamin D related compounds and processes for their preparation
Fujishima et al.	2000	Efficient synthesis and biological evaluation of all A-ring diastereomers of 1α, 25-dihydroxyvitamin D3 and its 20-epimer
KR20040095237A (ko)	2004-11-12	1α-히드록시-2-메틸렌-19-노르-호모프레그나칼시페롤의합성 방법
PL208188B1 (pl)	2011-03-31	Sposób otrzymywania kalcypotriolu
EP1047671B1 (de)	2003-12-10	Verfahren zur herstellung von cholecalciferol-derivaten und zwischenverbindungen
US5380720A (en)	1995-01-10	Iodo vitamin D3 compounds and method for preparing same
Kirihara et al.	2013	Synthesis of monofluoromethylcyclopropanes from alkenes without using freons: novel synthesis of chlorofluoromethyl phenyl sulfide and its application in cyclopropanation
US5089647A (en)	1992-02-18	Method for preparing intermediates for the synthesis of steroid side chains in optically active form
US5371249A (en)	1994-12-06	Iodo vitamin D3 compounds and method for preparing same
CA2062520C (en)	1998-08-11	Synthesis of 1-alpha-hydroxy-secosterol compounds
Kosugi et al.	1989	Lewis acid-mediated carbon-carbon bond forming reaction using the Pummerer rearrangement products from chiral. BETA.-hydroxy sulfoxides.
US5446174A (en)	1995-08-29	1-β7,8-trihydroxy vitamin D2, 1β7,8-trihydroxy vitamin D.sub.
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