Preparation of Oxysterols by C-H Oxidation of Dibromocholestane with Ru(Bpga) Catalyst

被引：3

作者：

Fujii, Yui ^{[1
]}

Yoritate, Makoto ^{[1
]}

Makino, Kana ^{[1
]}

Igawa, Kazunobu ^{[2
]}

Takeda, Daiki ^{[1
]}

Doiuchi, Daiki ^{[3
]}

Tomooka, Katsuhiko ^{[2
]}

Uchida, Tatsuya ^{[3
]}

Hirai, Go ^{[1
]}

机构：

[1] Kyushu Univ, Grad Sch Pharmaceut Sci, Higashi Ku, 3-1-1 Maidashi, Fukuoka, Fukuoka 8128582, Japan

[2] Kyushu Univ, Inst Mat Chem & Engn, Integrated Res Consortium Chem Sci IRCCS, Kasuga, Fukuoka 8168580, Japan

[3] Kyushu Univ, Grad Sch Sci, Dept Chem, Nishi Ku, 744 Motooka, Fukuoka, Fukuoka 8190395, Japan

来源：

MOLECULES | 2022年 / 27卷 / 01期

关键词：

cholesterol; oxysterol; C-H oxidation; Ru (bpga); 25-hydroxycholesterol; dihydroxycholesterol; GENE-EXPRESSION; C-25;

D O I：

10.3390/molecules27010225

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

Seven mono- and dihydroxycholesterols were prepared by direct C-H oxidation of the cholestane skeleton with a recently developed Ru(Bpga) catalyst (Ru(Bpga) = [RuCl (bpga) (PPh3)] Cl; bpga = 2-(bis(pyridin-2-ylmethyl)amino)-N-(2,6-dimethylphenyl)acetamide)). Due to the high selectivity of the Ru(Bpga) complex for tertiary C-H, the reaction afforded a mixture of 25-, 20-, 17-, and 14-oxygenated cholesterols that could be easily separated by high-performance liquid chromatography. These results suggest that late-stage C-H oxidation could be a viable strategy for preparing candidate metabolites of biologically important molecules.

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页数：10

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共 31 条

[1] FUNCTIONALIZATION OF SATURATED-HYDROCARBONS .3. THE OXIDATION OF 3-BETA,5-ALPHA,6-BETA-TRIACETOXYCHOLESTANE USING THE GIF SYSTEM [J].

BARTON, DHR ;

GOKTURK, AK ;

JANKOWSKI, K .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1985, (10) :2109-2117

[2] Are side-chain oxidized oxysterols regulators also in vivo? [J].

Bjorkhem, Ingemar .

JOURNAL OF LIPID RESEARCH, 2009, 50 :S213-S218

[3] OXIDATION OF NATURAL TARGETS BY DIOXIRANES .2. DIRECT HYDROXYLATION AT THE SIDE-CHAIN C-25 OF CHOLESTANE DERIVATIVES AND OF VITAMIN-D3 WINDAUS-GRUNDMANN KETONE [J].

BOVICELLI, P ;

LUPATTELLI, P ;

MINCIONE, E ;

PRENCIPE, T ;

CURCI, R .

JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (19) :5052-5054

[4] A predictably selective aliphatic C-H oxidation reaction for complex molecule synthesis [J].

Chen, Mark S. ;

White, M. Christina .

SCIENCE, 2007, 318 (5851) :783-787

[5] Assessment of brain cholesterol metabolism biomarker 24S-hydroxycholesterol in schizophrenia [J].

Chiappelli, Joshua ;

Quinton, Maria S. ;

Volfson, Dmitri ;

Cwik, Michael ;

Marshall, Wyatt ;

Bruce, Heather ;

Goldwaser, Eric ;

Kvarta, Mark ;

Summerfelt, Ann ;

Kochunov, Peter ;

O'Donnell, Patricio ;

Hong, Liyi Elliot .

NPJ SCHIZOPHRENIA, 2020, 6 (01)

[6] Oxysterol regulation of steroidogenic acute regulatory protein gene expression - Structural specificity and transcriptional and posttranscriptional actions [J].

Christenson, LK ;

McAllister, JM ;

Martin, KO ;

Javitt, NB ;

Osborne, TF ;

Strauss, JF .

JOURNAL OF BIOLOGICAL CHEMISTRY, 1998, 273 (46) :30729-30735

[7] Structure-Activity Relationships for Side Chain Oxysterol Agonists of the Hedgehog Signaling Pathway [J].

Corman, Audrey ;

DeBerardinis, Albert M. ;

Hadden, M. Kyle .

ACS MEDICINAL CHEMISTRY LETTERS, 2012, 3 (10) :828-833

[8] Catalytic Highly Regioselective C-H Oxygenation Using Water as the Oxygen Source: Preparation of 17O/18O-Isotope-Labeled Compounds [J].

Doiuchi, Daiki ;

Uchida, Tatsuya .

ORGANIC LETTERS, 2021, 23 (18) :7301-7305

[9] Non-Heme-Type Ruthenium Catalyzed Chemo- and Site-Selective C-H Oxidation [J].

Doiuchi, Daiki ;

Nakamura, Tatsuya ;

Hayashi, Hiroki ;

Uchida, Tatsuya .

CHEMISTRY-AN ASIAN JOURNAL, 2020, 15 (06) :762-765

[10] Microbial transformation of cholesterol: reactions and practical aspects-an update [J].

Giorgi, Victoria ;

Menendez, Pilar ;

Garcia-Carnelli, Carlos .

WORLD JOURNAL OF MICROBIOLOGY & BIOTECHNOLOGY, 2019, 35 (09)

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