200636-54-0

Usage

Uses

Used in Organometallic and Coordination Chemistry:
Phosphine oxide, [(2Z)-2-[(3R,4R,5R)-3,5-bis[[(1,1-diMethylethyl)diMethylsilyl]oxy]-4-[3-[[(1,1-diMethylethyl)diMethylsilyl]oxy]propoxy]-2-Methylenecyclohexylidene]ethyl]diphenylis used as a ligand in organometallic and coordination chemistry for its unique steric and electronic properties. The presence of the phosphine oxide group and bulky substituents may enable the formation of stable complexes with metal ions, facilitating various catalytic and coordination processes.
Used in Organic Synthesis:
In the field of organic synthesis, Phosphine oxide, [(2Z)-2-[(3R,4R,5R)-3,5-bis[[(1,1-diMethylethyl)diMethylsilyl]oxy]-4-[3-[[(1,1-diMethylethyl)diMethylsilyl]oxy]propoxy]-2-Methylenecyclohexylidene]ethyl]diphenylcan be employed as a reagent or intermediate in the synthesis of various organic compounds. Its complex structure and functional groups may allow for selective reactions and the formation of novel organic products.
Used in Materials Science:
Phosphine oxide, [(2Z)-2-[(3R,4R,5R)-3,5-bis[[(1,1-diMethylethyl)diMethylsilyl]oxy]-4-[3-[[(1,1-diMethylethyl)diMethylsilyl]oxy]propoxy]-2-Methylenecyclohexylidene]ethyl]diphenylmay find applications in materials science due to its potential to form self-assembled structures or contribute to the development of new materials with unique properties. Phosphine oxide, [(2Z)-2-[(3R,4R,5R)-3,5-bis[[(1,1-diMethylethyl)diMethylsilyl]oxy]-4-[3-[[(1,1-diMethylethyl)diMethylsilyl]oxy]propoxy]-2-Methylenecyclohexylidene]ethyl]diphenyl-'s steric hindrance and functional groups could play a role in the self-assembly process or the formation of supramolecular structures with potential applications in nanotechnology, sensors, or other advanced materials.

Synthetic route

{2-[(3R,4R,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-propoxy]-2-methylene-cyclohex-(Z)-ylidene]-ethyl}-diphenyl-phosphane → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
With dihydrogen peroxide
With dihydrogen peroxide In chloroform for 0.0166667h;	86 mg
With dihydrogen peroxide In tetrahydrofuran; chloroform; water at 20℃; for 0.5h;	33.8 mg

((Z)-2-((3R,4R,5R)-3,5-bis((tert-butyldimethylsilyl)oxy)-4-(3-((tert-butyldiphenylsilyl)oxy)propoxy)-2-methylenecyclohexylidene)ethyl)diphenylphosphine oxide (1254276-84-0) + t-butyldimethylsiyl triflate (69739-34-0) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Stage #1: (Z)-[2-{(3R,4R,5R)-3,5-bis(tert-butyldimethylsilanyloxy)-2-methylene-4-(3-(tert-butyldiphenylsilanyloxy)propoxy)cyclohexylidene}ethyl]diphenylphosphine oxide With tetrabutyl ammonium fluoride In tetrahydrofuran Inert atmosphere; Stage #2: t-butyldimethylsiyl triflate With N-ethyl-N,N-diisopropylamine In dichloromethane Inert atmosphere;	70%

{2-[(3R,4R,5R)-3,5-Bis-(tert-butyl-dimethyl-silanyloxy)-4-[3-(tert-butyl-dimethyl-silanyloxy)-propoxy]-2-methylene-cyclohex-(Z)-ylidene]-ethyl}-diphenyl-phosphane → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
With dihydrogen peroxide
With dihydrogen peroxide In chloroform for 0.0166667h;	86 mg
With dihydrogen peroxide In tetrahydrofuran; chloroform; water at 20℃; for 0.5h;	33.8 mg

[3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-(3-hydroxypropoxy)-2-methylenecyclohexylidene]ethanol (342644-91-1) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: 57 percent / NCS; Me2S / CH2Cl2 / 0.67 h 2: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 3: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 4: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

[3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]-1-chloroethane (200636-50-6) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 2 steps 1: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 2: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme
Multi-step reaction with 2 steps 2: H2O2 View Scheme

[3R-(1Z,3β,4α,5α)]-2-[5-(1,1-dimethylethyl)dimethylsilyloxy-3,4-isopropylidenedioxy-2-methylenecyclohexylidene]ethanol (244278-87-3) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions

Yield

Multi-step reaction with 9 steps 1: 83 percent / pyridine; DMAP / CH2Cl2 / 1 h / 0 °C 2: 82 percent / CSA; (+)-10-camphorsulfonic acid / methanol / 3 h / 20 °C 3: 96 percent / imidazole / dimethylformamide / 3 h / 0 °C 4: 88 percent / Me4NOH; aq. NaOH / toluene / 72 h / 20 °C 5: 91 percent / LiAlH4 / tetrahydrofuran / 0.25 h / 0 °C 6: 57 percent / NCS; Me2S / CH2Cl2 / 0.67 h 7: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 8: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 9: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

[3R-(1Z,3β,4α,5α)]-2-[3,4,5-trihydroxy-2-methylenecyclohexylidene]ethyl trimethylacetate (377091-68-4) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions

Yield

Multi-step reaction with 7 steps 1: 96 percent / imidazole / dimethylformamide / 3 h / 0 °C 2: 88 percent / Me4NOH; aq. NaOH / toluene / 72 h / 20 °C 3: 91 percent / LiAlH4 / tetrahydrofuran / 0.25 h / 0 °C 4: 57 percent / NCS; Me2S / CH2Cl2 / 0.67 h 5: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 6: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 7: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

[3R-(1Z,3β,4α,5α)]-2-[5-(1,1-dimethylethyl)dimethylsilyloxy-3,4-isopropylidenedioxy-2-methylenecyclohexylidene]ethyl trimethylacetate (342644-83-1) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions

Yield

Multi-step reaction with 8 steps 1: 82 percent / CSA; (+)-10-camphorsulfonic acid / methanol / 3 h / 20 °C 2: 96 percent / imidazole / dimethylformamide / 3 h / 0 °C 3: 88 percent / Me4NOH; aq. NaOH / toluene / 72 h / 20 °C 4: 91 percent / LiAlH4 / tetrahydrofuran / 0.25 h / 0 °C 5: 57 percent / NCS; Me2S / CH2Cl2 / 0.67 h 6: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 7: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 8: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

[3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-hydroxy-2-methylenecyclohexylidene]ethyl trimethylacetate (342644-90-0) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: 88 percent / Me4NOH; aq. NaOH / toluene / 72 h / 20 °C 2: 91 percent / LiAlH4 / tetrahydrofuran / 0.25 h / 0 °C 3: 57 percent / NCS; Me2S / CH2Cl2 / 0.67 h 4: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 5: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 6: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

[3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-(3-hydroxypropoxy)-2-methylenecyclohexylidene]-1-chloroethane (342645-82-3) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 2: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 3: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

[3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[2-(ethoxycarbonyl)ethoxy]-2-methylenecyclohexylidene]ethyl trimethylacetate (342645-81-2) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: 91 percent / LiAlH4 / tetrahydrofuran / 0.25 h / 0 °C 2: 57 percent / NCS; Me2S / CH2Cl2 / 0.67 h 3: 92 percent / imidazole / dimethylformamide / 0.25 h / 20 °C 4: n-BuLi / hexane; tetrahydrofuran / 0.33 h / -50 °C 5: 86 mg / aq. H2O2 / CHCl3 / 0.02 h View Scheme

tert-butyldimethylsilyl chloride (18162-48-6) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 7 steps 2: DDQ 3: 1.) Red-Al, 2.) I2 4: Pd(PPh3)4, Et3N 5: NCS, Me2SO / CH2Cl2 7: H2O2 View Scheme

lithium diphenylphosphide (65567-06-8, 4541-02-0) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 2 steps 2: H2O2 View Scheme

(2R,3S,4RS)-4-pivaloyloxy-3-(3-pivaloyloxypropoxy)-5-hexene-1,2-diol (337970-24-8) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 10 steps 1: PPh3, DEAd 2: 65 percent 3: NaOH / H2O 5: DDQ 6: 1.) Red-Al, 2.) I2 7: Pd(PPh3)4, Et3N 8: NCS, Me2SO / CH2Cl2 10: H2O2 View Scheme

(3RS,4R,5R)-4-(3-hydroxypropoxy)-9-(p-methoxyphenylmethoxy)non-1-en-7-yne-3,5-diol (933779-88-5) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 7 steps 2: DDQ 3: 1.) Red-Al, 2.) I2 4: Pd(PPh3)4, Et3N 5: NCS, Me2SO / CH2Cl2 7: H2O2 View Scheme

(2R,3S,4RS)-1,2-epoxy-4-pivaloyloxy-3-(3-pivaloyloxypropoxy)-5-hexene (200636-30-2) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 9 steps 1: 65 percent 2: NaOH / H2O 4: DDQ 5: 1.) Red-Al, 2.) I2 6: Pd(PPh3)4, Et3N 7: NCS, Me2SO / CH2Cl2 9: H2O2 View Scheme

(2R,3S,4RS)-1,2-O-isopropylidene-4-pivaloyloxy-3-(3-pivaloyloxypropoxy)-5-hexene-1,2-diol (337970-23-7) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 11 steps 1: aq. HCl 2: PPh3, DEAd 3: 65 percent 4: NaOH / H2O 6: DDQ 7: 1.) Red-Al, 2.) I2 8: Pd(PPh3)4, Et3N 9: NCS, Me2SO / CH2Cl2 11: H2O2 View Scheme

(5R,6R,7RS)-5,7-bis(tert-butyldimethylsilyloxy)-6-(3-tert-butyldimethylsilyloxypropoxy)non-8-en-2-yn-1-ol (933779-90-9) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 5 steps 1: 1.) Red-Al, 2.) I2 2: Pd(PPh3)4, Et3N 3: NCS, Me2SO / CH2Cl2 5: H2O2 View Scheme

(Z,5R,6R,7RS)-5,7-bis(tert-butyldimethylsilyloxy)-6-(3-tert-butyldimethylsilyloxypropoxy)-3-iodonona-2,8-dien-1-ol (200636-38-0) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 4 steps 1: Pd(PPh3)4, Et3N 2: NCS, Me2SO / CH2Cl2 4: H2O2 View Scheme

2,2-Dimethyl-propionic acid (2R,3R)-2-[3-(2,2-dimethyl-propionyloxy)-propoxy]-3-hydroxy-7-(4-methoxy-benzyloxy)-1-vinyl-hept-5-ynyl ester (200636-33-5) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 8 steps 1: NaOH / H2O 3: DDQ 4: 1.) Red-Al, 2.) I2 5: Pd(PPh3)4, Et3N 6: NCS, Me2SO / CH2Cl2 8: H2O2 View Scheme

1-{(R)-5,7-Bis-(tert-butyl-dimethyl-silanyloxy)-6-[3-(tert-butyl-dimethyl-silanyloxy)-propoxy]-non-8-en-2-ynyloxymethyl}-4-methoxy-benzene → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 6 steps 1: DDQ 2: 1.) Red-Al, 2.) I2 3: Pd(PPh3)4, Et3N 4: NCS, Me2SO / CH2Cl2 6: H2O2 View Scheme

2,2-Dimethyl-propionic acid 3-[(S)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-hydroxy-but-3-enyloxy]-propyl ester (200636-28-8) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 12 steps 1: Et3N 2: aq. HCl 3: PPh3, DEAd 4: 65 percent 5: NaOH / H2O 7: DDQ 8: 1.) Red-Al, 2.) I2 9: Pd(PPh3)4, Et3N 10: NCS, Me2SO / CH2Cl2 12: H2O2 View Scheme

(Z)-2-[(3R,4R,5R)-3,5-bis(tert-butyldimethylsilyloxy)-4-(3-tert-butyldimethylsilyloxypropoxy)-2-methylenecyclohexylidene]ethanol (200636-42-6) → [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0)

Conditions	Yield
Multi-step reaction with 3 steps 1: NCS, Me2SO / CH2Cl2 3: H2O2 View Scheme

[3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0) + (S)-2-[(1R,3aR,7aR)-octahydro-7a-methyl-4-oxo-4H-inden-1-yl]propyl 4-methylbenzenesulfonate (342645-83-4) → (1α,2β,3β,5Z,7E,20S)-1,3-bis[(1,1-dimethylethyl)dimethyl-silyloxy]-2-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-9,10-secopregna-5,7,10(19)-triene-20-methyl 4-methylbenzenesulfonate (342645-07-2)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; toluene at -50℃; for 0.5h;	66%

25-[(triethylsilyl)oxy]de-A,B-cholestan-8-one (144848-24-8) + [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0) → (5Z,7E)-(1R,2R,3R)-1,3-bis(tert-butyldimethylsilyloxy)-2-(3-tert-butyldimethylsilyloxypropoxy)-25-triethylsilyloxy-9,10-secocholesta-5,7,10(19)-triene (933779-95-4)

Conditions	Yield
Stage #1: [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Lythgoe coupling; Stage #2: 25-[(triethylsilyl)oxy]de-A,B-cholestan-8-one In tetrahydrofuran; hexane at -78℃; for 4h; Further stages.;	15%

25-[(triethylsilyl)oxy]de-A,B-cholestan-8-one (144848-24-8) + [3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0) → Eldecalcitol (104121-92-8)

Conditions	Yield
Multistep reaction;

[3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0) → (1β,2α,3α,5Z,7E)-1,3-bis[(1,1-dimethylethyl)dimethylsilyloxy]-2-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-25-trimethylsilyloxy-9,10-secocholesta-5,7,10(19)-triene (342645-84-5)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: 66 percent / n-butyllithium / tetrahydrofuran; toluene / 0.5 h / -50 °C 2.1: Mg / tetrahydrofuran / 0.5 h / 20 °C 2.2: 89 percent / CuBr*Me2S / tetrahydrofuran / 0.5 h / -10 °C View Scheme

[3R-(1Z,3β,4α,5α)]-[2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-2-methylenecyclohexylidene]ethyl]diphenylphosphine oxide (200636-54-0) → Eldecalcitol (104121-92-8)

Conditions	Yield
Multi-step reaction with 3 steps 1.1: 66 percent / n-butyllithium / tetrahydrofuran; toluene / 0.5 h / -50 °C 2.1: Mg / tetrahydrofuran / 0.5 h / 20 °C 2.2: 89 percent / CuBr*Me2S / tetrahydrofuran / 0.5 h / -10 °C 3.1: 96 percent / HF/pyridine / tetrahydrofuran / 20 °C View Scheme

Upstream product

• 200636-30-2 (2R,3S,4RS)-1,2-epoxy-4-pivaloyloxy-3-(3-pivaloyloxypropoxy)-5-hexene 
• 200636-28-8 2,2-Dimethyl-propionic acid 3-[(S)-1-((R)-2,2-dimethyl-[1,3]dioxolan-4-yl)-2-hydroxy-but-3-enyloxy]-propyl ester 
• 1254276-84-0 (Z)-[2-{(3R,4R,5R)-3,5-bis(tert-butyldimethylsilanyloxy)-2-methylene-4-(3-(tert-butyldiphenylsilanyloxy)propoxy)cyclohexylidene}ethyl]diphenylphosphine oxide 
• 69739-34-0 t-butyldimethylsiyl triflate 
• 200636-33-5 2,2-Dimethyl-propionic acid (2R,3R)-2-[3-(2,2-dimethyl-propionyloxy)-propoxy]-3-hydroxy-7-(4-methoxy-benzyloxy)-1-vinyl-hept-5-ynyl ester 
• 337970-23-7 (2R,3S,4RS)-1,2-O-isopropylidene-4-pivaloyloxy-3-(3-pivaloyloxypropoxy)-5-hexene-1,2-diol 
• 933779-88-5 (3RS,4R,5R)-4-(3-hydroxypropoxy)-9-(p-methoxyphenylmethoxy)non-1-en-7-yne-3,5-diol 
• 337970-24-8 (2R,3S,4RS)-4-pivaloyloxy-3-(3-pivaloyloxypropoxy)-5-hexene-1,2-diol 
• 65567-06-8 lithium diphenylphosphide 
• 18162-48-6 tert-butyldimethylsilyl chloride 
• 342645-81-2 [3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-[2-(ethoxycarbonyl)ethoxy]-2-methylenecyclohexylidene]ethyl trimethylacetate 
• 342645-82-3 [3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-(3-hydroxypropoxy)-2-methylenecyclohexylidene]-1-chloroethane 
• 342644-90-0 [3R-(1Z,3β,4α,5α)]-2-[3,5-bis[(1,1-dimethylethyl)dimethylsilyloxy]-4-hydroxy-2-methylenecyclohexylidene]ethyl trimethylacetate 
• 342644-83-1 [3R-(1Z,3β,4α,5α)]-2-[5-(1,1-dimethylethyl)dimethylsilyloxy-3,4-isopropylidenedioxy-2-methylenecyclohexylidene]ethyl trimethylacetate 

Downstream Products

• 342645-07-2 (1α,2β,3β,5Z,7E,20S)-1,3-bis[(1,1-dimethylethyl)dimethyl-silyloxy]-2-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-9,10-secopregna-5,7,10(19)-triene-20-methyl 4-methylbenzenesulfonate 
• 342645-84-5 (1β,2α,3α,5Z,7E)-1,3-bis[(1,1-dimethylethyl)dimethylsilyloxy]-2-[3-[(1,1-dimethylethyl)dimethylsilyloxy]propoxy]-25-trimethylsilyloxy-9,10-secocholesta-5,7,10(19)-triene 
• 104121-92-8 Eldecalcitol 

Relevant academic research and scientific papers

Synthesis of 2α-and 2β-substituted-14-epi-previtamin D 3 and their genomic activity

2α-and 2α-Substituted analogs of 14-epi-previtamin D3 were synthesized and isolated after thermal isomerization of 14-epi-vitamin D3 triene at 80 °C.The VDR binding affinity and transactivation activity of osteocalcin promoter in HOS cells were tested, and the 2a-methyl-substituted analog was found to have greater genomic activity than 14-epi-previtamin D 3.We found that modification at the C2 position of the seco-steroidal skeleton afforded interesting effects for biological genomic activity for the pre-vitamin D form as well as the natural vitamin D form.

Two convergent approaches to the synthesis of 1,25-dihydroxy 2-(3-hydroxypropoxy)vitamin D3 (ED-71) by the lythgoe and thf trost coupling reactions

Two convergent syntheses of 1,25-dihydroxy-2-(3-hydroxypropoxy)vitamin D3 (ED-71) by the Lythgoe coupling reaction between the A-ring phosphine oxide and the C/D-ring ketone and the Trost coupling reaction between the A-ring ene-yne and the C/D-ring bromomethylene are described.

Parallel synthesis of a vitamin D3 library in the solid-phase

A highly efficient synthesis of the vitamin D3 system on solid support is described. Two synthetic strategies for the solid-phase synthesis of vitamin D3 were developed. One is for 11-hydroxy analogues, and the other is for most other synthetic analogues. In the latter strategy, the sulfonate-linked CD-ring 58 was initially immobilized on PS-DES resin to give solid-supported CD-ring 63 (Scheme 10). Similarly, solid-supported CD-ring 63 was prepared by attachment of the CD-ring 10 to the chlorosulfonate resin 64. The vitamin D3 system was synthesized by Horner-Wadsworth-Emmons reaction of the A-ring phosphine oxide to a solid-supported CD-ring, followed by simultaneous introduction of the side chain and cleavage from resin with a Cu1-catalyzed Grignard reagent. Parallel synthesis of the vitamin D3 analogues was accomplished by a split and pool methodology utilizing radio frequency encoded combinatorial chemistry, and a manual parallel synthesizer for side chain diversification and deprotection. Additionally, we demonstrated the synthesis of various A-rings in a similar protocol for efficient preparation of building blocks.

Convergent synthesis of 1α,25-dihydroxy-2β-(3-hydroxypropoxy)vitamin D3 (ED-71)

A convergent and versatile synthesis of the potent vitamin D analog, 1α,25-dihydroxy-2β-(3-hydroxypropoxy)vitamin D3 [1] (ED-71) is described.