合成路线1
该中间体在本合成路线中的序号:
(C) By condensation of 5-(4-methoxy-2,3,6-trimethylphenyl)-3-methylpenta-2,4-diene-1-triphenylphosphonium bromide (I) with 3-formylcrotonic acid butyl ester (II) by means of NaH in DMF to yield 9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethylnona-2,4,6,8-tetraen-1-oic acid butyl ester (III), which is then hydrolyzed with KOH in refluxing ethanol - water.
The starting products (I) and (II) are obtained as follows:
1) The methylation of 2,3,5-trimethylphenol (IV) with KOH and methyl iodide in refluxing aqueous ethanol gives 2,3,5-trimethylanisole (V), which is then carbonylated with POCl3 and DMF (A) to afford 4-methoxy-2,3,6-trimethylbenzaldehyde (VI). The condensation of (VI) with acetone (B) by means of NaOH gives 4-(4-methoxy-2,3,6-trimethylphenyl)-3-buten-2-one (VII), which by a Grignard reaction with ethynylmagnesium bromide (C) in THF is converted into 5-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-3-hydroxy-4-penten-1-yne (VIII). The controlled hydrogenation of (VIII) with H2 over a Pd catalyst in hexane yields 5-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-3-hydroxy-1,4-pentadiene (IX), which is finally treated with triphenylphosphonium bromide in benzene at 60 C to give the phosphonium salt (I).
2) The oxidation of dibutyl L-(+)-tartrate (X) with lead tetraacetate in benzene gives butyl glyoxalate (XI), which is then condensed with propionic aldehyde (D) by means of dibutylamine (E) to afford ester (II).
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(D) |
15966 |
propionaldehyde
|
123-38-6 |
C3H6O |
详情 | 详情
|
(B) |
23199 |
2-Propanone; Acetone; beta-ketopropane; chevron acetone;propan-2-one; Dimethyl formaldehyde; Dimethyl ketone; dimethylketal; Ketone propane; Methyl ketone; Propanone; Pyroacetic acid; Pyroacetic ether |
67-64-1 |
C3H6O |
详情 | 详情
|
(A) |
33491 |
Dimethylformamide
|
68-12-2 |
C3H7NO |
详情 | 详情
|
(E) |
33492 |
N,N-dibutylamine; N-butyl-1-butanamine
|
111-92-2 |
C8H19N |
详情 | 详情
|
(I) |
33485 |
[(2E,4E)-5-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-2,4-pentadienyl](triphenyl)phosphonium bromide
|
|
C34H36BrOP |
详情 |
详情
|
(II) |
33486 |
butyl (E)-3-methyl-4-oxo-2-butenoate
|
|
C9H14O3 |
详情 |
详情
|
(III) |
33487 |
butyl (2E,4E,6E,8E)-9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethyl-2,4,6,8-nonatetraenoate
|
|
C25H34O3 |
详情 |
详情
|
(IV) |
33479 |
2,3,5-trimethylphenol
|
697-82-5 |
C9H12O |
详情 | 详情
|
(V) |
33480 |
1-methoxy-2,3,5-trimethylbenzene; methyl 2,3,5-trimethylphenyl ether
|
20469-61-8 |
C10H14O |
详情 | 详情
|
(VI) |
33481 |
4-methoxy-2,3,6-trimethylbenzaldehyde
|
|
C11H14O2 |
详情 |
详情
|
(VII) |
33482 |
(E)-4-(4-methoxy-2,3,6-trimethylphenyl)-3-buten-2-one
|
54757-47-0 |
C14H18O2 |
详情 | 详情
|
(VIII) |
33483 |
(E)-1-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-1-penten-4-yn-3-ol
|
|
C16H20O2 |
详情 |
详情
|
(IX) |
33484 |
(1E)-1-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-1,4-pentadien-3-ol
|
|
C16H22O2 |
详情 |
详情
|
(X) |
33490 |
Dibutyl tartrate
|
87-92-3 |
C12H22O6 |
详情 | 详情
|
(XI) |
30937 |
butyl 2-oxoacetate
|
|
C6H10O3 |
详情 |
详情
|
(C) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
合成路线2
该中间体在本合成路线中的序号:
(C) The methylation of 2,3,5-trimethylphenol (I) with MeI and KOH in 10% aqueous ethanol gives 2,3,5-trimethylanisole (II), which is formylated with DMF and POCl3 yielding 2,3,6-trimethyl-p-anisylaldehyde (III). The condensation of (III) with acetone (B) by means of NaOH affords 4-(4-methoxy-2,3,6-trimethylphenyl)but-3-en-2-one (IV), which by a Grignard reaction with ethynylmagnesium bromide (C) in THF is converted into the acetylenic alcohol (V). Partial hydrogenation of (V) with H2 over Pd/C in hexane gives dienic alcohol (VI), which is condensed with triphenylphosphine hydrobromide in benzene affording 5-(4-methoxy-2,3,6 trimethylphenyl)-3-methylpenta-2,4-diene-1-triphenylphosphonium bromide (VII). A Wittig condensation of (VII) with butyl 3-formylcrotonate (VIII) by means of NaH in DMF gives butyl 9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethylnona-2,4,6,8-tetraenoate (IX), which is hydrolyzed with KOH in refluxing ethanol-water yielding the corresponding free acid (X). This acid is converted into the acyl chloride (XI) by treatment with PCl3 in refluxing benzene. Finally, this compound is treated with ethylamine (E) in ether.
The butyl 3-formylcrotonate (VIII) is obtained as follows: The oxidation of dibutyl tartrate (XII) with lead tetraacetate in benzene gives butyl glyoxalate (XIII), which is then condensed with propionaldehyde (XIV) by heating at 110 C with dibutyl-amine (D).
【1】
Bollag, W.; et al.; Polyene derivatives. BE 0813002; FR 2223037; GB 1468401; GB 1468402 .
|
【2】
Bollag, W.; et al.; Antidandruff compositions containing 9-(4-lower alkoxy-2,3,6-trilower-alkylphenyl)-3,7-dimethyl-nona-2,4,6,8-tetraen-1-oic acid lower alkyl amides. DE 2542366; ES 441173; FR 2330381; GB 1504350; JP 51057840; US 4021574 .
|
【3】
Castaner, J.; Hillier, K.; Motretinide. Drugs Fut 1978, 3, 2, 126.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(E) |
10928 |
Ethanamine
|
75-04-7 |
C2H7N |
详情 | 详情
|
(B) |
23199 |
2-Propanone; Acetone; beta-ketopropane; chevron acetone;propan-2-one; Dimethyl formaldehyde; Dimethyl ketone; dimethylketal; Ketone propane; Methyl ketone; Propanone; Pyroacetic acid; Pyroacetic ether |
67-64-1 |
C3H6O |
详情 | 详情
|
(A) |
33491 |
Dimethylformamide
|
68-12-2 |
C3H7NO |
详情 | 详情
|
(D) |
33492 |
N,N-dibutylamine; N-butyl-1-butanamine
|
111-92-2 |
C8H19N |
详情 | 详情
|
(I) |
33479 |
2,3,5-trimethylphenol
|
697-82-5 |
C9H12O |
详情 | 详情
|
(II) |
33480 |
1-methoxy-2,3,5-trimethylbenzene; methyl 2,3,5-trimethylphenyl ether
|
20469-61-8 |
C10H14O |
详情 | 详情
|
(III) |
33481 |
4-methoxy-2,3,6-trimethylbenzaldehyde
|
|
C11H14O2 |
详情 |
详情
|
(IV) |
33482 |
(E)-4-(4-methoxy-2,3,6-trimethylphenyl)-3-buten-2-one
|
54757-47-0 |
C14H18O2 |
详情 | 详情
|
(V) |
33483 |
(E)-1-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-1-penten-4-yn-3-ol
|
|
C16H20O2 |
详情 |
详情
|
(VI) |
33484 |
(1E)-1-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-1,4-pentadien-3-ol
|
|
C16H22O2 |
详情 |
详情
|
(VII) |
33485 |
[(2E,4E)-5-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-2,4-pentadienyl](triphenyl)phosphonium bromide
|
|
C34H36BrOP |
详情 |
详情
|
(VIII) |
33486 |
butyl (E)-3-methyl-4-oxo-2-butenoate
|
|
C9H14O3 |
详情 |
详情
|
(IX) |
33487 |
butyl (2E,4E,6E,8E)-9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethyl-2,4,6,8-nonatetraenoate
|
|
C25H34O3 |
详情 |
详情
|
(X) |
33488 |
(2E,4E,6E,8E)-9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethyl-2,4,6,8-nonatetraenoic acid
|
|
C21H26O3 |
详情 |
详情
|
(XI) |
33489 |
(2E,4E,6E,8E)-9-(4-methoxy-2,3,6-trimethylphenyl)-3,7-dimethyl-2,4,6,8-nonatetraenoyl chloride
|
|
C21H25ClO2 |
详情 |
详情
|
(XII) |
33490 |
Dibutyl tartrate
|
87-92-3 |
C12H22O6 |
详情 | 详情
|
(XIII) |
30937 |
butyl 2-oxoacetate
|
|
C6H10O3 |
详情 |
详情
|
(XIV) |
15966 |
propionaldehyde
|
123-38-6 |
C3H6O |
详情 | 详情
|
(C) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
合成路线3
该中间体在本合成路线中的序号:
(C) The reaction of 2,3,5-trimethylanisole (II) [prepared by alkylation of 2,3,5-trimethylphenol (I) with methyl iodide] with DMF and POCl3 affords 4-(4-methoxy-2,3,6-trimethylbenzaldehyde (V), which is condensed with propanone (B) in aqueous NaOH giving 4-(4-methoxy-2,3,6-trimethylphenyl)-but-3-en-2-one (VI). The Grignard reaction of (VI) with ethynylmagnesium bromide (C) in THF yields 5-(4-methoxy-2,3,6-trimethylphe-nyl)-3-methyl-3-hydroxypenta-4-en-1-yne (VII), which is partially hydrogenated with H2 over deactivated Pd in hexane to give 5-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-3-hydroxypenta-1,4-diene (VIII). The reaction of (VIII) with triphenylphosphonium hydrobromide in benzene affords 5-(4-methoxy-2,3,6-trimethylphenyl)-3-methylpenta-2,4-diene-1-triphenylphosphonium bromide (IX). Finally, this compound is submitted to a Wittig reaction with ethyl 3,4-formylcrotonate (D) in DMF (NaH is used as base).
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(B) |
33481 |
4-methoxy-2,3,6-trimethylbenzaldehyde
|
|
C11H14O2 |
详情 |
详情
|
(D) |
40061 |
ethyl (E)-3-methyl-4-oxo-2-butenoate
|
62054-49-3 |
C7H10O3 |
详情 | 详情
|
(I) |
33479 |
2,3,5-trimethylphenol
|
697-82-5 |
C9H12O |
详情 | 详情
|
(II) |
33480 |
1-methoxy-2,3,5-trimethylbenzene; methyl 2,3,5-trimethylphenyl ether
|
20469-61-8 |
C10H14O |
详情 | 详情
|
(V) |
23199 |
2-Propanone; Acetone; beta-ketopropane; chevron acetone;propan-2-one; Dimethyl formaldehyde; Dimethyl ketone; dimethylketal; Ketone propane; Methyl ketone; Propanone; Pyroacetic acid; Pyroacetic ether |
67-64-1 |
C3H6O |
详情 | 详情
|
(VI) |
33482 |
(E)-4-(4-methoxy-2,3,6-trimethylphenyl)-3-buten-2-one
|
54757-47-0 |
C14H18O2 |
详情 | 详情
|
(VII) |
33483 |
(E)-1-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-1-penten-4-yn-3-ol
|
|
C16H20O2 |
详情 |
详情
|
(VIII) |
33484 |
(1E)-1-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-1,4-pentadien-3-ol
|
|
C16H22O2 |
详情 |
详情
|
(IX) |
33485 |
[(2E,4E)-5-(4-methoxy-2,3,6-trimethylphenyl)-3-methyl-2,4-pentadienyl](triphenyl)phosphonium bromide
|
|
C34H36BrOP |
详情 |
详情
|
(C) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
合成路线4
该中间体在本合成路线中的序号:
(III) The reaction of ethyl 3-(3-furyl)acrylate (I) with the cuprate t-Bu2CuCNLi2, followed by reduction with diisobutylaluminum hydride gives the tert-butylated aldehyde (II), which is condensed with ethynylmagnesium bromide (III), yielding a mixture of the syn and anti acetylenic alcohols (IV) and (V). After chromatographic separation, the undesired anti-alcohol (IV) is converted to the syn-alcohol (V) by a Mitsunobu inversion. Alcohol (V) was protected as the triethylsilyl ether and carboxylated with ethyl chloroformate affording the acetylenic ester (VI), which is cyclized with the zinc/copper enolate (VII) giving the 2-oxocyclopentenecarboxylate (VIII). The photocyclization of (VIII) with U.V. light (366 nm) yields the tetracyclic ester (IX), which is desilylated with HF and mesylated with mesyl chloride affording mesylate (X). Lactonization of (X) with PPTS gives the pentacyclic lactone (XI), which is dehydrogenated with PhSeCl and NaIO4 to the enone (XII). The opening of the cyclobutane ring of (XII) with dimethyldioxirane (DMDO) and TsOH yields the trihydroxy compound (XIII), which is treated with MeOH and TsOH to afford the bis(methyl)acetal (XIV). The deoxygenation of (XIV) through the corresponding xanthate and reduction with tributylstannane gives intermediate (XV), which is hydroxylated and acylated yielding the propionyl ester (XVI). Cyclization of (XVI) by means of LDA in THF followed by treatment with NaOMe affords a diastereomeric mixture (XVII), which is separated by chromatography. The isolated epimer (XVIII) was treated with MeOH and camphorsulfonic acid (CSA) resulting in the methanolysis of its lactone ring and formation of a new tetrahydrofuran ring providing the pentacyclic compound (XIX).
【1】
Crimmins, M.T.; et al.; The total synthesis of (±)-ginkgolide B. J Am Chem Soc 2000, 122, 35, 8453. |
【2】
Pace, J.M.; Watterson, S.H.; Nantermet, P.G.; Crimmins, M.T.; Kim-Meade, A.S.; Wagman, A.S.; Thomas, J.B.; Total synthesis of (±)-ginkgolide B. J Am Chem Soc 1999, 121, 43, 10249. |
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
37633 |
ethyl (E)-3-(3-furyl)-2-propenoate
|
|
C9H10O3 |
详情 |
详情
|
(II) |
37634 |
3-(3-furyl)-4,4-dimethylpentanal
|
|
C11H16O2 |
详情 |
详情
|
(III) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(IV) |
37635 |
(3R,5S)-5-(3-furyl)-6,6-dimethyl-1-heptyn-3-ol
|
|
C13H18O2 |
详情 |
详情
|
(V) |
37636 |
(3S,5S)-5-(3-furyl)-6,6-dimethyl-1-heptyn-3-ol
|
|
C13H18O2 |
详情 |
详情
|
(VI) |
37637 |
ethyl (4S,6S)-6-(3-furyl)-7,7-dimethyl-4-[(triethylsilyl)oxy]-2-octynoate
|
|
C22H36O4Si |
详情 |
详情
|
(VIII) |
37638 |
ethyl 2-[(1S,3S)-3-(3-furyl)-4,4-dimethyl-1-[(triethylsilyl)oxy]pentyl]-5-oxo-1-cyclopentene-1-carboxylate
|
|
C25H40O5Si |
详情 |
详情
|
(IX) |
37639 |
ethyl (1S,3S,6aR)-3-(tert-butyl)-7-oxo-1-[(triethylsilyl)oxy]-2,3,8,9-tetrahydro-1H,6aH-dicyclopenta[2,3:3,4]cyclobuta[1,2-b]furan-6b(7H)-carboxylate
|
|
C25H40O5Si |
详情 |
详情
|
(X) |
37640 |
ethyl (1S,3S,6aR)-3-(tert-butyl)-1-[(methylsulfonyl)oxy]-7-oxo-2,3,8,9-tetrahydro-1H,6aH-dicyclopenta[2,3:3,4]cyclobuta[1,2-b]furan-6b(7H)-carboxylate
|
|
C20H28O7S |
详情 |
详情
|
(XI) |
37641 |
|
|
C17H20O4 |
详情 |
详情
|
(XII) |
37642 |
|
|
C17H18O4 |
详情 |
详情
|
(XIII) |
37643 |
|
|
C17H22O7 |
详情 |
详情
|
(XIV) |
37644 |
|
|
C19H26O7 |
详情 |
详情
|
(XV) |
37645 |
|
|
C19H26O6 |
详情 |
详情
|
(XVI) |
37646 |
|
|
C22H30O8 |
详情 |
详情
|
(XVII) |
37647 |
|
|
C22H30O8 |
详情 |
详情
|
(XVIII) |
37648 |
|
|
C22H30O8 |
详情 |
详情
|
(XIX) |
37649 |
|
|
C22H30O8 |
详情 |
详情
|
合成路线5
该中间体在本合成路线中的序号:
(B) 18-Methyl-4-oestrene-3,17-dione (I) is hydroxylated by fermentation with Penicillium raistrickii giving the 15alpha-hydroxy compound (II), which is ketalized with 2,2-dimethylpropanediol (A), triethyl orthoformate and p-toluenesulfonic acid in CH2Cl2 giving a mixture of the DELTA(5-6) and DELTA(5-10)-ketals (IIIa-b). These ketals are mesylated witn methanesulfonyl chloride in pyridine yielding the mesyl ester (IVa-b), which is treated with sodium acetate in DMF to afford the oestradiene ketal (Va-b). Finally, this compound is treated with ethynylmagnesium bromide (B) and refluxed with oxalic acid (C) in methanol.
【1】
Hofmeister, H.; Wiechert, R.; Annen, K.; Laurent, H.; Steinbeck, H.; Steroids and pharmaceutical compositions thereof. BE 0847090; FR 2326927; GB 1569135; JP 52046060; US 4081537 .
|
【2】
Castaner, J.; Blancafort, P.; Gestodene. Drugs Fut 1977, 2, 12, 805.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(A) |
12641 |
Neopentyl glycol; 2,2-Dimethyl-1,3-propanediol
|
126-30-7 |
C5H12O2 |
详情 | 详情
|
(B) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(IIIa) |
33952 |
|
|
C24H36O4 |
详情 |
详情
|
(IIIb) |
33953 |
|
|
C24H36O4 |
详情 |
详情
|
(IVa) |
33954 |
|
|
C27H42O4S |
详情 |
详情
|
(IVb) |
33955 |
|
|
C27H42O4S |
详情 |
详情
|
(Va) |
33956 |
|
|
C24H34O3 |
详情 |
详情
|
(Vb) |
33957 |
|
|
C24H34O3 |
详情 |
详情
|
(I) |
33950 |
(8R,9S,10R,13S,14S)-13-ethyl-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene-3,17(2H,6H)-dione
|
|
C19H26O2 |
详情 |
详情
|
(II) |
33951 |
(8R,9S,10R,13S,14S,15S)-13-ethyl-15-hydroxy-7,8,9,10,11,12,13,14,15,16-decahydro-1H-cyclopenta[a]phenanthrene-3,17(2H,6H)-dione
|
|
C19H26O3 |
详情 |
详情
|
(C) |
15713 |
Oxalic acid
|
144-62-7 |
C2H2O4 |
详情 | 详情
|
合成路线6
该中间体在本合成路线中的序号:
(B) Ketals (IIIa-b) can also be treated with trimethylsilyl chloride in pyridine to give the trimethylsilyl derivative (VIa-b), which is then treated with ethynylmagnesium bromide (B) and oxalic acid (C) in methanol.
【1】
Hofmeister, H.; Wiechert, R.; Annen, K.; Laurent, H.; Steinbeck, H.; Steroids and pharmaceutical compositions thereof. BE 0847090; FR 2326927; GB 1569135; JP 52046060; US 4081537 .
|
【2】
Castaner, J.; Blancafort, P.; Gestodene. Drugs Fut 1977, 2, 12, 805.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(B) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(IIIa) |
33952 |
|
|
C24H36O4 |
详情 |
详情
|
(IIIb) |
33953 |
|
|
C24H36O4 |
详情 |
详情
|
(VIa) |
33958 |
|
|
C27H44O4Si |
详情 |
详情
|
(VIb) |
33959 |
|
|
C27H44O4Si |
详情 |
详情
|
(C) |
15713 |
Oxalic acid
|
144-62-7 |
C2H2O4 |
详情 | 详情
|
合成路线7
该中间体在本合成路线中的序号:
(B) Ketals (IIIa-b) can also be acetylated with acetic anhydride in pyridine to the acetate (VIIa-b), which is then treated with ethynylmagnesium bromide (B) and oxalic acid (C) in methanol.
【1】
Hofmeister, H.; Wiechert, R.; Annen, K.; Laurent, H.; Steinbeck, H.; Steroids and pharmaceutical compositions thereof. BE 0847090; FR 2326927; GB 1569135; JP 52046060; US 4081537 .
|
【2】
Castaner, J.; Blancafort, P.; Gestodene. Drugs Fut 1977, 2, 12, 805.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(B) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(IIIa) |
33952 |
|
|
C24H36O4 |
详情 |
详情
|
(IIIb) |
33953 |
|
|
C24H36O4 |
详情 |
详情
|
(VIIa) |
33960 |
|
|
C26H38O5 |
详情 |
详情
|
(VIIb) |
33961 |
|
|
C26H38O5 |
详情 |
详情
|
(C) |
15713 |
Oxalic acid
|
144-62-7 |
C2H2O4 |
详情 | 详情
|
合成路线8
该中间体在本合成路线中的序号:
(IV) Racemic compound.- The reaction of 1,1-diacetylcyclopropane (I) with the disilylated propargyl alcohol (II) by means of tert-butyllithium gives the monocondensation compound (III), which is treated with ethynylmagnesium bromide (IV) and CeCl3 to yield the bis acetylenic diol (V). The acylation of (V) with acetic anhydridde affords the monoacetate (VI), which is isomerized by means of [CuH(PPh3]6 to provide the allene compound (VII). The selective deprotection of (VII) gives the terminal acetylene (VIII), which is cyclized with Mo(CO)6 in refluxing DMSO/toleuene to afford the tricyclic ketone (IX). The methyletion of (IX) with CH3Li gives the monosilylated tricyclic diol (X), which is deprotected with TBAF yielding the diol (XI). The oxidation of the secondary alcohol of (XI) with Dess Martin periodinane (DMP) provides the tricyclic ketone (XII), which is finally hydroxymethylated with formaldehyde and sulfuric acid to afford the target compound as a racemic mixture.
【1】
Brummond, K.M.; Lu, J.; A short synthesis of the potent antitumor agent (±)-hydroxymethylacylfulvene using allenic pauson-khand type cycloaddition. J Am Chem Soc 1999, 121, 21, 5087. |
【2】
Brummond, K.M.; et al.; A rapid synthesis of hydroxymethylacylfulvene (HMAF) using the allenic Pauson - Khand reaction. A synthetic approach to either enantiomer of this illudane structure. J Am Chem Soc 2000, 122, 20, 4915.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
27116 |
1-(1-acetylcyclopropyl)-1-ethanone
|
|
C7H10O2 |
详情 |
详情
|
(II) |
27117 |
tert-butyl(dimethyl)silyl 3-(trimethylsilyl)-2-propynyl ether
|
|
C12H26OSi2 |
详情 |
详情
|
(III) |
27118 |
1-[1-[2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-ethanone
|
|
C19H36O3Si2 |
详情 |
详情
|
(IV) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(V) |
27119 |
3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-hydroxy-1-methyl-2-propynyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol
|
|
C21H38O3Si2 |
详情 |
详情
|
(VI) |
27120 |
1-[1-[2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-methyl-2-propynyl acetate
|
|
C23H40O4Si2 |
详情 |
详情
|
(VII) |
27121 |
3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol
|
|
C21H38O2Si2 |
详情 |
详情
|
(VIII) |
27122 |
3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-4-pentyn-2-ol
|
|
C18H30O2Si |
详情 |
详情
|
(IX) |
27123 |
4'-(Tert-butyldimethylsilyloxy)-5'-hydroxy-5',7'-dimethyl-2',4',5',6'-tetrahydro-1'H-spiro[cyclopropane-1,6'-inden]-2'-one
|
|
C19H30O3Si |
详情 |
详情
|
(X) |
27124 |
7'-(Tert-butyldimethylsilyloxy)-2',4',6'-trimethyl-6',7'-dihydro-5'H-spiro[cyclopropane-1,5'-inden]-6'-ol
|
|
C20H32O2Si |
详情 |
详情
|
(XI) |
27125 |
2',4',6'-Trimethyl-6',7'-dihydro-5'H-spiro[cyclopropane-1,5'-indene]-6',7'-diol
|
|
C14H18O2 |
详情 |
详情
|
(XII) |
27126 |
6'-Hydroxy-2',4',6'-trimethyl-6',7'-dihydro-5'H-spiro[cyclopropane-1,5'-inden]-7'-one
|
|
C14H16O2 |
详情 |
详情
|
合成路线9
该中间体在本合成路线中的序号:
(VII) The chiral 6(R) isomer of 213351 has been obtained as follows:
The condensation of 1,1-diacetylcyclopropane monoethylene ketal (I) with acetylenic phosphonate (II) by means of NaHMDS in THF gives the silylated pentenyne (III), which is treated with TsOH in acetone/water yielding the acetylcyclopropane (IV). The Sharpless asymetric dihydroxylation of the double bond of (IV) by means of chiral auxiliary (DHQD)2PYR, K2OsO2(OH)4, K3Fe(CN)6 and K2CO3 in tert-butanol/water affords the chiral diol (V), which is monosilylated with TBDMS-OTf providing the silyl ether (VI). The condensation of (VI) with ethynylmagnesium bromide (VII) and CeCl3 gives the diacetylenic diol (VIII), which is regioselectively acetylated with Ac2O, TEA and DMAP yielding the monoacetate (IX). The treatment of the propargylic acetate (IX) with [(PPh3)CuH]6 in methanol affords the allene (X), which is regioselectively desilylated at the terminal acetylenic group furnishing the cyclization precursor (XI). The Mo(CO)6 promoted cyclization of (XI) in refluxing toluene/DMSO gives the chiral tricyclic ketone (XII). The methylation of (XII) with MeLi yields the monosilylated diol (XIII), which is desilylated with TBAF to the chiral diol (XIV). The oxidation of (XIV) with Dess Martin periodinane (DMP) affords the chiral hydroyketone (XV), which is finally hydroxymethylated with formaldehyde and H2SO4 to furnish the target compound.
【1】
Brummond, K.M.; et al.; A rapid synthesis of hydroxymethylacylfulvene (HMAF) using the allenic Pauson - Khand reaction. A synthetic approach to either enantiomer of this illudane structure. J Am Chem Soc 2000, 122, 20, 4915.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
36876 |
1-[1-(2-methyl-1,3-dioxolan-2-yl)cyclopropyl]-1-ethanone
|
|
C9H14O3 |
详情 |
详情
|
(II) |
36877 |
diethyl 3-(trimethylsilyl)-2-propynylphosphonate
|
|
C10H21O3PSi |
详情 |
详情
|
(III) |
36878 |
trimethyl[(Z)-4-[1-(2-methyl-1,3-dioxolan-2-yl)cyclopropyl]-3-penten-1-ynyl]silane
|
|
C15H24O2Si |
详情 |
详情
|
(IV) |
36879 |
1-[1-[(Z)-1-methyl-4-(trimethylsilyl)-1-buten-3-ynyl]cyclopropyl]-1-ethanone
|
|
C13H20OSi |
详情 |
详情
|
(V) |
36880 |
1-[1-[(1R,2R)-1,2-dihydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-ethanone
|
|
C13H22O3Si |
详情 |
详情
|
(VI) |
36881 |
1-[1-[(1R,2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-ethanone
|
|
C19H36O3Si2 |
详情 |
详情
|
(VII) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(VIII) |
36882 |
(2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-hydroxy-1-methyl-2-propynyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol
|
|
C21H38O3Si2 |
详情 |
详情
|
(IX) |
36883 |
1-[1-[(1R,2R)-2-[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-1-methyl-4-(trimethylsilyl)-3-butynyl]cyclopropyl]-1-methyl-2-propynyl acetate
|
|
C23H40O4Si2 |
详情 |
详情
|
(X) |
36884 |
(2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-5-(trimethylsilyl)-4-pentyn-2-ol
|
|
C21H38O2Si2 |
详情 |
详情
|
(XI) |
36888 |
(2R,3R)-3-[[tert-butyl(dimethyl)silyl]oxy]-2-[1-(1-methyl-1,2-propadienyl)cyclopropyl]-4-pentyn-2-ol
|
|
C18H30O2Si |
详情 |
详情
|
(XII) |
36885 |
|
|
C19H30O3Si |
详情 |
详情
|
(XIII) |
36886 |
|
|
C20H32O2Si |
详情 |
详情
|
(XIV) |
36887 |
|
|
C14H18O2 |
详情 |
详情
|
(XV) |
26689 |
6(R)-6-Hydroxy-2,4,6-trimethyl-6,7-dihydro-5H-spiro[indene-5,1'-cyclopropan]-7-one; 6(R)-6-Hydroxy-2,4,6-trimethyl-6,7-dihydro-5H-spiro[indene-5,1'-cyclopropan]-7-one
|
|
C14H16O2 |
详情 |
详情
|
合成路线10
该中间体在本合成路线中的序号:
(XII) The boron enolate aldol condensation between aldehyde (IX) and the chiral oxazolidinone (II) affords adduct (X). After conversion to the Weinreb amide (XI), addition of magnesium acetylide (XII) leads to alkynone (XIII). Diastereoselective reduction of (XIII) using DIBAL in THF furnishes diol (XIV) as the major isomer. After protection of diol (XIV) as the bis-silyl ether (XV), hydroboration of its triple bond with catecholborane, followed by alkaline work-up gives rise to the boronic acid fragment (XVI).
【1】
Evans, D.A.; Starr, J.T.; A cascade cycloaddition strategy leading to the total synthesis of (-)-FR182877. Angew Chem. Int Ed 2002, 41, 10, 1787.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(II) |
25713 |
(4S)-4-benzyl-3-propionyl-1,3-oxazolidin-2-one
|
|
C13H15NO3 |
详情 |
详情
|
(IX) |
60351 |
4-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-2-butenal
|
|
C20H24O2Si |
详情 |
详情
|
(X) |
60353 |
3-(6-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-3-hydroxy-2-methyl-4-hexenoyl)-4-(phenylmethyl)-1,3-oxazolidin-2-one
|
|
C33H39NO5Si |
详情 |
详情
|
(XI) |
60354 |
6-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-3-hydroxy-N,2-dimethyl-N-(methyloxy)-4-hexenamide
|
|
C25H35NO4Si |
详情 |
详情
|
(XII) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(XIII) |
60355 |
8-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-5-hydroxy-4-methyl-6-octen-1-yn-3-one
|
|
C25H30O3Si |
详情 |
详情
|
(XIV) |
60356 |
8-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-4-methyl-6-octen-1-yne-3,5-diol
|
|
C25H32O3Si |
详情 |
详情
|
(XV) |
60357 |
4,6-bis{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-5-methyl-2-octen-7-ynyl (1,1-dimethylethyl)(diphenyl)silyl ether; 8-{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-10-ethynyl-2,2,9,12,12,13,13-heptamethyl-3,3-diphenyl-4,11-dioxa-3,12-disila-6-tetradecene
|
|
C37H60O3Si3 |
详情 |
详情
|
(XVI) |
60358 |
3,5-bis{[(1,1-dimethylethyl)(dimethyl)silyl]oxy}-8-{[(1,1-dimethylethyl)(diphenyl)silyl]oxy}-4-methyl-1,6-octadienylboronic acid
|
|
C37H63BO5Si3 |
详情 |
详情
|
合成路线11
该中间体在本合成路线中的序号:
(II) Treatment of quinoline (I) with ethynylmagnesium bromide (II) in THF at low temperature, and then with 4-chlorophenyl chloroformate (III) gave carbamate (IV). Subsequent deprotection of tert-butyldimethylsilyl group with p-toluenesulfonic acid yielded allyl alcohol (V), and this was stereoselectively epoxidized with m-chloroperbenzoic acid to give epoxyalcohol (VI). Coupling of (VI) with vinyl chloride (VII) in the presence of Pd(0)-CuI catalyst provided the enediyne compound (VIII). This was oxidized with Dess-Martin periodinane reagent to the aldehyde (IX). Finally, CsF-promoted cyclization in the presence of acetic anhydride provided the title compound as a 2:1 mixture of diastereoisomers, which could not be separated.
【1】
Unno, R.; et al.; Structure-activity relationships of cyclic enediynes related to dynemicin A-I. Synthesis and antitumor activity of 9-acetoxy enediynes equipped with aryl carbamate moieties. Bioorg Med Chem 1997, 5, 5, 883.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
17777 |
tert-butyl(dimethyl)silyl 4-quinolinylmethyl ether; 4-([[tert-butyl(dimethyl)silyl]oxy]methyl)quinoline
|
|
C16H23NOSi |
详情 |
详情
|
(II) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(III) |
17779 |
1-chloro-4-[(chlorocarbonyl)oxy]benzene
|
7693-45-0 |
C7H4Cl2O2 |
详情 | 详情
|
(IV) |
17780 |
4-chlorophenyl (2R)-4-([[tert-butyl(dimethyl)silyl]oxy]methyl)-2-ethynyl-1(2H)-quinolinecarboxylate
|
|
C25H28ClNO3Si |
详情 |
详情
|
(V) |
17781 |
4-chlorophenyl (2R)-2-ethynyl-4-(hydroxymethyl)-1(2H)-quinolinecarboxylate
|
|
C19H14ClNO3 |
详情 |
详情
|
(VI) |
17782 |
4-chlorophenyl (1aS,2S,7bS)-2-ethynyl-7b-(hydroxymethyl)-1a,7b-dihydrooxireno[2,3-c]quinoline-3(2H)-carboxylate
|
|
C19H14ClNO4 |
详情 |
详情
|
(VII) |
17783 |
[(Z)-4-chloro-3-buten-1-ynyl](trimethyl)silane
|
|
C7H11ClSi |
详情 |
详情
|
(VIII) |
17784 |
4-chlorophenyl (1aS,2S,7bS)-7b-(hydroxymethyl)-2-[(Z)-6-(trimethylsilyl)-3-hexene-1,5-diynyl]-1a,7b-dihydrooxireno[2,3-c]quinoline-3(2H)-carboxylate
|
|
C26H24ClNO4Si |
详情 |
详情
|
(IX) |
17785 |
4-chlorophenyl (1aS,2S,7bR)-7b-formyl-2-[(Z)-6-(trimethylsilyl)-3-hexene-1,5-diynyl]-1a,7b-dihydrooxireno[2,3-c]quinoline-3(2H)-carboxylate
|
|
C26H22ClNO4Si |
详情 |
详情
|
合成路线12
该中间体在本合成路线中的序号:
(III) Aldehyde (II) was prepared by mono-benzylation of 1,4-butanediol (I) followed by Swern oxidation. Subsequent addition of ethynylmagnesium bromide (III) to the aldehyde function of (II) provided propargyl alcohol (IV). Kinetic resolution of the racemic alcohol (IV) by lipase-mediated acetylation in the presence of vinyl acetate produced a mixture of the (S)-acetate (V) and the unreacted (R)-alcohol (VI). The required (S)-propargyl acetate (V) was subjected to partial hydrogenation using Lindlar catalyst to furnish allyl acetate (VII), which was further hydrolyzed to the chiral alcohol (VIII). After protection of (VIII) as the silylated derivative (IX), reductive removal of the benzyl ether using lithium naphthalenide afforded the primary alcohol (X). This was then treated with methanesulfonyl chloride and triethylamine to give mesylate (XI). Ozonolysis of the double bond of (XI), followed by reductive work-up with dimethyl sulfide, yielded aldehyde (XII). This was reacted with hydroxylamine hydrochloride and Et3N in allyl alcohol (XIII) to produce the intermediate nitrone (XIV), which underwent simultaneous 1,3-dipolar cycloaddition to allyl alcohol to furnish the isoxazolopyridine (XV) as a mixture of three diastereoisomers. This mixture was then subjected to hydrogenolytic N-O bond fission, producing piperidine (XVI).
【1】
Ooi, H.e; et al.; A concise enantioselective synthesis of antimalarial febrifugine alkaloids. Org Lett 2001, 3, 6, 953.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
43160 |
1,4-butanediol;1,4-Dihydroxybutane;1,4-Butylene glycol;Tetramethylene glycol |
110-63-4 |
C4H10O2 |
详情 | 详情
|
(II) |
46170 |
4-(benzyloxy)butanal
|
|
C11H14O2 |
详情 |
详情
|
(III) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(IV) |
47833 |
6-(benzyloxy)-1-hexyn-3-ol
|
|
C13H16O2 |
详情 |
详情
|
(V) |
47834 |
(1S)-1-[3-(benzyloxy)propyl]-2-propynyl acetate
|
|
C15H18O3 |
详情 |
详情
|
(VI) |
47835 |
(3R)-6-(benzyloxy)-1-hexyn-3-ol
|
|
C13H16O2 |
详情 |
详情
|
(VII) |
47836 |
(1S)-1-[3-(benzyloxy)propyl]-2-propenyl acetate
|
|
C15H20O3 |
详情 |
详情
|
(VIII) |
47837 |
(3S)-6-(benzyloxy)-1-hexen-3-ol
|
|
C13H18O2 |
详情 |
详情
|
(IX) |
47838 |
([(1S)-1-[3-(benzyloxy)propyl]-2-propenyl]oxy)(tert-butyl)diphenylsilane; benzyl (4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-hexenyl ether
|
|
C29H36O2Si |
详情 |
详情
|
(X) |
47839 |
(4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-hexen-1-ol
|
|
C22H30O2Si |
详情 |
详情
|
(XI) |
47840 |
(4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-hexenyl methanesulfonate
|
|
C23H32O4SSi |
详情 |
详情
|
(XII) |
47841 |
(4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-oxopentyl methanesulfonate
|
|
C22H30O5SSi |
详情 |
详情
|
(XIII) |
12234 |
2-Propen-1-ol; Allyl alcohol
|
107-18-6 |
C3H6O |
详情 | 详情
|
(XIV) |
47842 |
(5S)-5-[[tert-butyl(diphenyl)silyl]oxy]-2,3,4,5-tetrahydro-1-pyridiniumolate
|
|
C21H27NO2Si |
详情 |
详情
|
(XV) |
47843 |
((4S)-4-[[tert-butyl(diphenyl)silyl]oxy]hexahydro-2H-isoxazolo[2,3-a]pyridin-2-yl)methanol
|
|
C24H33NO3Si |
详情 |
详情
|
(XVI) |
47844 |
3-((3S)-3-[[tert-butyl(diphenyl)silyl]oxy]piperidinyl)-1,2-propanediol
|
|
C24H35NO3Si |
详情 |
详情
|
合成路线13
该中间体在本合成路线中的序号:
(III) Aldehyde (II) was prepared by mono-benzylation of 1,4-butanediol (I) followed by Swern oxidation. Subsequent addition of ethynylmagnesium bromide (III) to the aldehyde function of (II) provided propargyl alcohol (IV). Kinetic resolution of the racemic alcohol (IV) by lipase-mediated acetylation in the presence of vinyl acetate produced a mixture of the (S)-acetate (V) and the unreacted (R)-alcohol (VI). The required (S)-propargyl acetate (V) was subjected to partial hydrogenation using Lindlar catalyst to furnish allyl acetate (VII), which was further hydrolyzed to the chiral alcohol (VIII). After protection of (VIII) as the silylated derivative (IX), reductive removal of the benzyl ether using lithium naphthalenide afforded the primary alcohol (X). This was then treated with methanesulfonyl chloride and triethylamine to give mesylate (XI). Ozonolysis of the double bond of (XI), followed by reductive work-up with dimethyl sulfide, yielded aldehyde (XII). This was reacted with hydroxylamine hydrochloride and Et3N in allyl alcohol (XIII) to produce the intermediate nitrone (XIV), which underwent simultaneous 1,3-dipolar cycloaddition to allyl alcohol to furnish the isoxazolopyridine (XV) as a mixture of three diastereoisomers. This mixture was then subjected to hydrogenolytic N-O bond fission, producing piperidine (XVI).
【1】
Ooi, H.e; et al.; A concise enantioselective synthesis of antimalarial febrifugine alkaloids. Org Lett 2001, 3, 6, 953.
|
中间体序号 |
中间体编号 |
品名 |
CAS号 |
分子式 |
供应商 |
用于合成 |
(I) |
43160 |
1,4-butanediol;1,4-Dihydroxybutane;1,4-Butylene glycol;Tetramethylene glycol |
110-63-4 |
C4H10O2 |
详情 | 详情
|
(II) |
46170 |
4-(benzyloxy)butanal
|
|
C11H14O2 |
详情 |
详情
|
(III) |
17778 |
ETHYNYLMAGNESIUM BROMIDE; bromo(ethynyl)magnesium
|
4301-14-8 |
C2HBrMg |
详情 | 详情
|
(IV) |
47833 |
6-(benzyloxy)-1-hexyn-3-ol
|
|
C13H16O2 |
详情 |
详情
|
(V) |
47834 |
(1S)-1-[3-(benzyloxy)propyl]-2-propynyl acetate
|
|
C15H18O3 |
详情 |
详情
|
(VI) |
47835 |
(3R)-6-(benzyloxy)-1-hexyn-3-ol
|
|
C13H16O2 |
详情 |
详情
|
(VII) |
47836 |
(1S)-1-[3-(benzyloxy)propyl]-2-propenyl acetate
|
|
C15H20O3 |
详情 |
详情
|
(VIII) |
47837 |
(3S)-6-(benzyloxy)-1-hexen-3-ol
|
|
C13H18O2 |
详情 |
详情
|
(IX) |
47838 |
([(1S)-1-[3-(benzyloxy)propyl]-2-propenyl]oxy)(tert-butyl)diphenylsilane; benzyl (4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-hexenyl ether
|
|
C29H36O2Si |
详情 |
详情
|
(X) |
47839 |
(4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-hexen-1-ol
|
|
C22H30O2Si |
详情 |
详情
|
(XI) |
47840 |
(4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-hexenyl methanesulfonate
|
|
C23H32O4SSi |
详情 |
详情
|
(XII) |
47841 |
(4S)-4-[[tert-butyl(diphenyl)silyl]oxy]-5-oxopentyl methanesulfonate
|
|
C22H30O5SSi |
详情 |
详情
|
(XIII) |
12234 |
2-Propen-1-ol; Allyl alcohol
|
107-18-6 |
C3H6O |
详情 | 详情
|
(XIV) |
47842 |
(5S)-5-[[tert-butyl(diphenyl)silyl]oxy]-2,3,4,5-tetrahydro-1-pyridiniumolate
|
|
C21H27NO2Si |
详情 |
详情
|
(XV) |
47843 |
((4S)-4-[[tert-butyl(diphenyl)silyl]oxy]hexahydro-2H-isoxazolo[2,3-a]pyridin-2-yl)methanol
|
|
C24H33NO3Si |
详情 |
详情
|
(XVI) |
47844 |
3-((3S)-3-[[tert-butyl(diphenyl)silyl]oxy]piperidinyl)-1,2-propanediol
|
|
C24H35NO3Si |
详情 |
详情
|