JPS6150951B2 - - Google Patents
Info
- Publication number
- JPS6150951B2 JPS6150951B2 JP56051506A JP5150681A JPS6150951B2 JP S6150951 B2 JPS6150951 B2 JP S6150951B2 JP 56051506 A JP56051506 A JP 56051506A JP 5150681 A JP5150681 A JP 5150681A JP S6150951 B2 JPS6150951 B2 JP S6150951B2
- Authority
- JP
- Japan
- Prior art keywords
- benzyl
- trimethylsilyl
- tetra
- chloroform
- nmr
- Prior art date
- Legal status (The legal status 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 status listed.)
- Expired
Links
- 150000002596 lactones Chemical class 0.000 claims description 7
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 claims description 7
- 150000001241 acetals Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000002009 diols Chemical class 0.000 claims description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 16
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- GRRNUXAQVGOGFE-UHFFFAOYSA-N Hygromycin-B Natural products OC1C(NC)CC(N)C(O)C1OC1C2OC3(C(C(O)C(O)C(C(N)CO)O3)O)OC2C(O)C(CO)O1 GRRNUXAQVGOGFE-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000002772 monosaccharides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000002905 orthoesters Chemical class 0.000 description 3
- GRRNUXAQVGOGFE-SVNOMHMPSA-N (3'r,3as,4s,4's,5'r,6r,6'r,7s,7as)-4-[(1s,2r,3s,5r,6s)-3-amino-2,6-dihydroxy-5-(methylamino)cyclohexyl]oxy-6'-[(1s)-1-amino-2-hydroxyethyl]-6-(hydroxymethyl)spiro[4,6,7,7a-tetrahydro-3ah-[1,3]dioxolo[4,5-c]pyran-2,2'-oxane]-3',4',5',7-tetrol Chemical compound O[C@H]1[C@H](NC)C[C@H](N)[C@@H](O)[C@@H]1O[C@H]1[C@H]2OC3([C@@H]([C@@H](O)[C@@H](O)[C@@H]([C@@H](N)CO)O3)O)O[C@H]2[C@@H](O)[C@@H](CO)O1 GRRNUXAQVGOGFE-SVNOMHMPSA-N 0.000 description 2
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- -1 clamycin Chemical compound 0.000 description 2
- ZKQFHRVKCYFVCN-UHFFFAOYSA-N ethoxyethane;hexane Chemical compound CCOCC.CCCCCC ZKQFHRVKCYFVCN-UHFFFAOYSA-N 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229930192734 Avilamycin Natural products 0.000 description 1
- 239000004190 Avilamycin Substances 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- IHGNORNGVOUHBM-UHFFFAOYSA-N Flambamycin Natural products COCC1OC(OC2C(C3OC4(OC3CO2)C2OCOC2C(O)(C(C)O4)C(C)=O)OC(=O)C(C)C)C(OC)C(O)C1OC(C1O)OC(C)C(OC)C1OC(C(C1(C)O2)O)OC(C)C1OC2(OC1C)CC(O)C1OC(OC1C)CC(O)C1OC(=O)C1=C(C)C(Cl)=C(O)C(Cl)=C1OC IHGNORNGVOUHBM-UHFFFAOYSA-N 0.000 description 1
- 229910003849 O-Si Inorganic materials 0.000 description 1
- 229910003872 O—Si Inorganic materials 0.000 description 1
- XILKGRFKVHSHRS-UHFFFAOYSA-N SS-56C Natural products OC1C(O)C(O)C(C(CO)N)OC11OC(C(O)C(CO)OC2OC3C(C(N)C(O)C(N)C3O)O)C2O1 XILKGRFKVHSHRS-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- ATJWHTJURZPAPG-CFNSFCSXSA-N [(1r,2r,4r,6s)-4-[(2r,2'r,3's,3ar,4r,4'r,6s,7s,7ar)-6-[(2r,3r,4r,5r,6s)-2-[(2r,3s,4s,5s,6s)-6-[(2r,3as,3'ar,6s,6'r,7r,7's,7ar,7'ar)-7'-acetyl-7'-hydroxy-6'-methyl-7-(2-methylpropanoyloxy)spiro[4,6,7,7a-tetrahydro-3ah-[1,3]dioxolo[4,5-c]pyran-2,4'-6,7a-dih Chemical compound O([C@@H]1[C@@H](C)C[C@H](C[C@H]1O)O[C@H]1[C@H](O)C[C@]2(O[C@@H]3[C@@H](C)O[C@H]([C@H]([C@@]3(C)O2)O)O[C@H]2[C@@H](OC)[C@@H](O)O[C@H]([C@@H]2O)O[C@H]2[C@H](O)[C@H](OC)[C@H](O[C@H]3[C@@H]([C@@H]4O[C@]5(O[C@H]4CO3)[C@@H]3OCO[C@H]3[C@@](O)([C@@H](C)O5)C(C)=O)OC(=O)C(C)C)O[C@@H]2COC)O[C@@H]1C)C(=O)C1=C(C)C(Cl)=C(O)C(Cl)=C1OC ATJWHTJURZPAPG-CFNSFCSXSA-N 0.000 description 1
- XIRGHRXBGGPPKY-OTPQUNEMSA-N [(2r,3s,4r,6s)-6-[(2'r,3's,3ar,4r,4'r,6s,7ar)-6-[(2s,3r,4r,5s,6r)-2-[(2r,3s,4s,5s,6s)-6-[(2r,3as,3'ar,6'r,7r,7's,7ar,7'ar)-7'-acetyl-7'-hydroxy-6'-methyl-7-(2-methylpropanoyloxy)spiro[4,6,7,7a-tetrahydro-3ah-[1,3]dioxolo[4,5-c]pyran-2,4'-6,7a-dihydro-3ah- Chemical compound O([C@H]1[C@H](O)C[C@@H](O[C@@H]1C)O[C@H]1[C@H](O)CC2(O[C@]3(C)C[C@@H](O[C@H](C)[C@H]3O2)O[C@H]2[C@@H](OC)[C@@H](C)O[C@H]([C@@H]2O)O[C@H]2[C@H](O)[C@H](OC)[C@H](OC3[C@@H]([C@@H]4O[C@]5(O[C@H]4CO3)[C@@H]3OCO[C@H]3[C@@](O)([C@@H](C)O5)C(C)=O)OC(=O)C(C)C)O[C@@H]2COC)O[C@@H]1C)C(=O)C1=C(C)C(Cl)=C(O)C(Cl)=C1OC XIRGHRXBGGPPKY-OTPQUNEMSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000002647 aminoglycoside antibiotic agent Substances 0.000 description 1
- 229960005185 avilamycin Drugs 0.000 description 1
- 235000019379 avilamycin Nutrition 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- GRRNUXAQVGOGFE-NZSRVPFOSA-N hygromycin B Chemical compound O[C@@H]1[C@@H](NC)C[C@@H](N)[C@H](O)[C@H]1O[C@H]1[C@H]2O[C@@]3([C@@H]([C@@H](O)[C@@H](O)[C@@H](C(N)CO)O3)O)O[C@H]2[C@@H](O)[C@@H](CO)O1 GRRNUXAQVGOGFE-NZSRVPFOSA-N 0.000 description 1
- 229940097277 hygromycin b Drugs 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Saccharide Compounds (AREA)
Description
本発明は新規なグリコシリデンアセタール類の
製造方法に関する。
オルトソマイシン系抗生物質には、エバニノミ
シンＢ、Ｃ、Ｄ、フランバマイシン、クラマイシ
ン、アビラマイシンなどのオリゴ糖抗生物と、デ
ストライシンＡ、Ｂ、Ｃ、ヒグロマイシンＢ、抗
生物質Ａ−396−Ｉ、SS−56Cなどのアミノ配糖
体抗生物質とがある。これらには共通して、アル
ドン酸のラクトンが他の単糖の２個の水酸基とア
セタール結合（スピロ環状オルトエステル結合）
した、全く新しい結合様式が含まれている。例と
して、以下にエバニノミシンＤとデストマイシン
Ａについて示す。なおオルトエステル炭素は
The present invention relates to a novel method for producing glycosidene acetals. Ortosomycin antibiotics include oligosaccharide antibiotics such as evaninomycin B, C, and D, flambamycin, clamycin, and avilamycin, and destricin A, B, and C, hygromycin B, and antibiotic A-396-. There are aminoglycoside antibiotics such as I and SS-56C. Common to these is that the lactone of the aldonic acid connects with two hydroxyl groups of other monosaccharides through an acetal bond (spirocyclic orthoester bond).
It includes a completely new binding style. As examples, Evaninomicin D and Destomycin A are shown below. In addition, orthoester carbon is
【式】で囲んで示した。
(1) エバニノミシンＤ
(2) デストマイシンＡ
このグリコシリデンアセタールの合成法として
は、アルドン酸のラクトンとエポキシドとの付加
反応による合成法と、ラクトンとジオール類を硫
酸触媒の存在下に脱水縮合させる方法が知られて
いるが、これらの反応では簡単なジオールでは目
的物が得られるものの、アルドン酸ラクトンと他
の単糖の２級水酸基が関与するアセタールの形成
には良い結果が得られなかつた。
本発明は、アルドン酸ラクトンとジオール類の
トリメチルシリルエーテルとをトリフルオロメタ
ンスルホン酸のトリメチルシリルエステル（トリ
メチルシリルトリフレート）を触媒として縮合さ
せグリコシリデンアセタールを合成するものであ
る。本発明の方法によれば、ジクロロメタンのよ
うな不活性溶媒中で室温で反応し、従来よりも好
収率で目的物が得られるだけでなく、上記の方法
では得られなかつた、単糖の２個の水酸基が関与
するアセタールも好収率で得られる。これは、下
記の反応式で示されるように、トリメチルシリル
基がトリメチルシリルトリフレート
（（CH3）3SiOSO2CF3）触媒によりシロキサン誘導
体（（CH3）3Si−Ｏ−Si（CH3）3）となつて系外に
出るためすみやかに反応が進行するためであり、
本方法は種々の五員環および六員環状アルドン酸
ラクトンに適用できる。
（式中、TMSはトリメチルシリル基を示し、
TMS+O-Tfはトリメチルシリルフレートを示
す。また、ジオールのＲは互いに結合して環を形
成してもよい。）
実施例 １
２・３・４・６−テトラ−Ｏ−ベンジル−Ｄ−
グルコン酸−１・５−ラクトン
（以降、式中のBnはベンジル基を示す。）
561mg（104ｍmol）とジ−Ｏ−トリメチルシリル
エタンジオール208mg（3.35ｍmol）をジクロロメ
タン３mlに溶かした溶液に、窒素気流下、−10℃
で、トリメチルシリルトリフレート
（TMSOTf）22mg（0.1ｍmol）を触媒として加
え、室温で２時間撹拌した。
反応溶液に乾燥ピリジン0.2mlを加えて中和
し、ジクロロメタン30mlで稀釈した後、有機層を
飽和炭酸水素ナトリウムおよび水で洗浄し、乾燥
後濃縮すると、１・２−Ｏ−（２・３・４・６−
テトラ−Ｏ−ベンジル−Ｄ−グルコピラノシリデ
ン）エタンジオール
が91.2％（553.7mg）の収率で得られた。
(1) 融点：51〜52℃
(2) 〔α〕D：＋51゜（c1.0、クロロホルム）
(3) 元素分析：
実測値 計算値（C36H38O7として）
Ｃ 73.59％ 74.20％
Ｈ 6.52％ 6.57％
(4) オルトエステル炭素の13C−NMR（ppm）シ
フト：119.63
実施例 ２
２・３・４・６−テトラ−Ｏ−ベンジル−Ｄ−
グルコン酸−１・５−ラクトン517.8mg（0.96ｍ
mol）とシクロヘキサン−１・２−シス−ジオー
ル388mg（3.34ｍmol）のジ−Ｏ−トリメチルシリ
ル誘導体とのジクロロメタン（３ml）溶液に、窒
素気流下で、触媒（TMSOTf）120mgを加え、室
温で72時間撹拌した。
実施例１と同様に後処理し、生成物をフラツシ
ユカラム（ヘキサン−エ−テル５：２）にかけて
分離し、１・２−Ｏ−（２・３・4.6−テトラ−Ｏ
−ベンジル−Ｄ−グルコシリデン）シクロヘキサ
ン−１・２−シス−ジオ−ルの２種の異性体ａ
（194mg、30.5％）およびｂ（378mg、59.5％）
を得た。
(イ) 異性体ａ
(1) 融点：58〜60℃
(2) 〔α〕D：＋45゜（c0.9、クロロホルム）
(3) 13C−NHR：119.6ppm
(4) 元素分析：
実測値 計算値（C40H44O7として）
Ｃ 75.72％ 75.45％
Ｈ 7.03％ 6.96％
(ロ) 異性体ｂ
(1) 融点：98〜100℃
(2) 〔α〕D：＋55゜（c1.1、クロロホルム）
(3) 13C−NMR：118.5ppm
(4) 元素分析：
実測値 計算値（C40H44O7として）
Ｃ 75.80％ 75.45％
Ｈ 7.12％ 6.96％
実施例 ３
２・３・４・６−テトラ−Ｏ−ベンジル−Ｄ−
グルコン酸−１・５−ラクトン1.85ｇ（1.85ｍ
mol）とシクロヘキサン−１・２−トランスジオ
ール358mg（3.08ｍmol）のジ−Ｏ−トリメチルシ
リル誘導体のジクロロメタン（３ml）溶液に
TMSOTf80mgを加え、窒素気流下、室温で26時
間撹拌した。
実施例１と同様に後処理して、１・２−Ｏ−
（２・３・４・６−テトラ−Ｏ−ベンジル−Ｄ−
グルコシリデン）シクロヘキサン−１・２−トラ
ンス−ジオールの２種の誘導体ａおよびｂ
を、30.6％（308mg）および33.3％（335.4mg）の
収率で得た。
(イ) 異性体ａ
(1) 融点：91〜93℃
(2) 〔α〕D：＋65゜（c0.8、クロロホルム）
(3) 13C−NMR：119.1ppm
(4) 元素分析：
実測値 計算値（C40H44O7として）
Ｃ 75.43％ 75.45％
Ｈ 7.02％ 6.96％
(ロ) 異性体ｂ
(1) シロツプ
(2) 〔α〕D：＋7.9゜（c0.5、クロロホルム）
(3) 13C−NMR：119.2ppm
(4) 元素分析：
実測値 計算値（C40H44O7として）
Ｃ 75.00％ 75.45％
Ｈ 7.11％ 6.96％
実施例 ４
２・３・４・６−テトラ−Ｏ−ベンジル−Ｄ−
グルコン酸−１・５−ラクトン667.5mg（1.24ｍ
mol）と
の２・３−ジ−Ｏ−トリメチルシリルエーテル
570.7mg（1.10ｍmol）とを同様に反応させメチル
−４・６−ジ−Ｏ−ベンジル−２・３−Ｏ−
（２・３・４・６−テトラ−Ｏ−ベンジル−Ｄ−
グルコピラノシリデン）−α−Ｄ−マンノピラノ
シド
の２種の異性体を、それぞれ44.8％（441mg）お
よび26.6％（262mg）の収率で得た。
(イ) 異性体ａ
(1) 融点：61〜62℃
(2) 〔α〕D：＋28.1゜（c0.6、クロロホルム）
(3) 13C−NMR：119.0ppm
(4) 元素分析：
実測値 計算値（C55H58O11として）
Ｃ 74.01％ 73.80％
Ｈ 6.57％ 6.53％
(ロ) 異性体ｂ
(1) シロツプ
(2) 〔α〕D：＋10.3゜（c0.2、クロロホルム）
(3) 13C−NMR：120.4ppm
(4) 元素分析：
実測値 計算値（C55H58O11として）
Ｃ 73.92％ 73.80％
Ｈ 6.51％ 6.53％
実施例 ５
δ−バレロラクトン１ｇ（10.0ｍmol）と
の２・３−ジ−Ｏ−トリメチルシリルエーテル
1.07ｇ（2.06ｍmol）のジクロロメタン（２ml）
溶液に、窒素気流下、−10〜−20℃でTMSOTf20
mgを加え、室温で５時間反応させた後、実施例１
と同様に後処理し、ついで生成物をフラツシユカ
ラム（ヘキサン−エーテル５：２）で分離精製し
て主生成物のみを40.2％の収率で得た。もう１つ
の異性体は微量で、オルトエステル炭素
119.0ppmの存在が13C−NMRで検知できるだけ
であつた。
メチル−４・６−ジ−Ｏ−ベンジル−２・３−
Ｏ−（テトラヒドロピラン−２−イリデン）−α−
Ｄ−マンノピラノシド
(1) 融点：40〜41.5℃
(2) 〔α〕D：＋44゜（c0.35、クロロホルム）
(3) 13C−NMR：118.5ppm
(4) 元素分析：
実測値 計算値（C26H32O7として）
Ｃ 68.19％ 68.40％
Ｈ 7.12％ 7.07％It is shown enclosed in [Formula]. (1) Evani Minicin D (2) Destomycin A Known methods for synthesizing this glycosylidene acetal include the addition reaction of aldonic acids with lactones and epoxides, and the dehydration condensation of lactones and diols in the presence of a sulfuric acid catalyst. Although the desired product could be obtained using a simple diol in the reaction, good results were not obtained in the formation of an acetal involving aldonic acid lactones and secondary hydroxyl groups of other monosaccharides. The present invention synthesizes a glycosylidene acetal by condensing an aldonic acid lactone and a trimethylsilyl ether of a diol using trimethylsilyl ester of trifluoromethanesulfonic acid (trimethylsilyl triflate) as a catalyst. According to the method of the present invention, the reaction is carried out at room temperature in an inert solvent such as dichloromethane, and not only can the desired product be obtained in a better yield than conventional methods, but also monosaccharides, which could not be obtained by the above methods, can be obtained. Acetals involving two hydroxyl groups are also obtained in good yields. As shown in the reaction formula below, the trimethylsilyl group is converted into a siloxane derivative (( CH3 ) 3Si - O-Si(CH3) 3 ) using a trimethylsilyl triflate (( CH3 ) 3SiOSO2CF3 ) catalyst . ), which causes the reaction to proceed quickly as it exits the system.
This method is applicable to a variety of five- and six-membered cyclic aldonic acid lactones. (In the formula, TMS represents a trimethylsilyl group,
TMS + O - Tf indicates trimethylsilylflate. Further, R of the diol may be bonded to each other to form a ring. ) Example 1 2,3,4,6-tetra-O-benzyl-D-
Gluconic acid-1,5-lactone (Hereinafter, Bn in the formula represents a benzyl group.) A solution of 561 mg (104 mmol) and 208 mg (3.35 mmol) of di-O-trimethylsilylethanediol dissolved in 3 ml of dichloromethane was added at -10°C under a nitrogen stream.
Then, 22 mg (0.1 mmol) of trimethylsilyl triflate (TMSOTf) was added as a catalyst, and the mixture was stirred at room temperature for 2 hours. The reaction solution was neutralized by adding 0.2 ml of dry pyridine and diluted with 30 ml of dichloromethane. The organic layer was washed with saturated sodium bicarbonate and water, dried and concentrated to give 1,2-O-(2,3, 4.6-
Tetra-O-benzyl-D-glucopyranosilidene) ethanediol was obtained with a yield of 91.2% (553.7 mg). (1) Melting point: 51-52℃ (2) [α] D : +51゜ (c1.0, chloroform) (3) Elemental analysis: Actual value Calculated value (as C 36 H 38 O 7 ) C 73.59% 74.20% H 6.52% 6.57% (4) 13 C-NMR (ppm) shift of orthoester carbon: 119.63 Example 2 2,3,4,6-tetra-O-benzyl-D-
Gluconic acid-1,5-lactone 517.8mg (0.96m
mol) and cyclohexane-1,2-cis-diol (388 mg (3.34 mmol)) of a di-O-trimethylsilyl derivative in dichloromethane (3 ml) under a nitrogen atmosphere, 120 mg of catalyst (TMSOTf) was added, and the mixture was heated at room temperature for 72 hours. Stirred. Work-up was carried out in the same manner as in Example 1, and the product was separated by applying a flash column (hexane-ether 5:2) to give 1,2-O-(2,3,4,6-tetra-O-
-benzyl-D-glucosylidene) cyclohexane-1,2-cis-diol two isomers a
(194 mg, 30.5%) and b (378 mg, 59.5%) I got it. (a) Isomer a (1) Melting point: 58-60℃ (2) [α] D : +45゜ (c0.9, chloroform) (3) 13 C-NHR: 119.6ppm (4) Elemental analysis: Actual value Calculated values (as C 40 H 44 O 7 ) C 75.72% 75.45% H 7.03% 6.96% (b) Isomer b (1) Melting point: 98-100℃ (2) [α] D : +55゜ (c1.1 , chloroform) (3) 13 C-NMR: 118.5 ppm (4) Elemental analysis: Actual value Calculated value (as C 40 H 44 O 7 ) C 75.80% 75.45% H 7.12% 6.96% Example 3 2.3.4・6-tetra-O-benzyl-D-
Gluconic acid-1,5-lactone 1.85g (1.85m
mol) and 358 mg (3.08 mmol) of cyclohexane-1,2-transdiol of di-O-trimethylsilyl derivative in dichloromethane (3 ml).
80 mg of TMSOTf was added, and the mixture was stirred at room temperature for 26 hours under a nitrogen stream. After treatment in the same manner as in Example 1, 1.2-O-
(2,3,4,6-tetra-O-benzyl-D-
Two derivatives a and b of cyclohexane-1,2-trans-diol (glucosylidene) were obtained in yields of 30.6% (308 mg) and 33.3% (335.4 mg). (a) Isomer a (1) Melting point: 91-93°C (2) [α] D : +65° (c0.8, chloroform) (3) 13 C-NMR: 119.1 ppm (4) Elemental analysis: Actual value Calculated value (as C 40 H 44 O 7 ) C 75.43% 75.45% H 7.02% 6.96% (b) Isomer b (1) Syrup (2) [α] D : +7.9° (c0.5, chloroform) (3) 13 C-NMR: 119.2 ppm (4) Elemental analysis: Actual value Calculated value (as C 40 H 44 O 7 ) C 75.00% 75.45% H 7.11% 6.96% Example 4 2.3.4.6- Tetra-O-benzyl-D-
Gluconic acid-1,5-lactone 667.5mg (1.24m
mol) and 2,3-di-O-trimethylsilyl ether of
570.7 mg (1.10 mmol) was reacted in the same manner to give methyl-4,6-di-O-benzyl-2,3-O-
(2,3,4,6-tetra-O-benzyl-D-
glucopyranosilidene)-α-D-mannopyranoside Two isomers of were obtained in yields of 44.8% (441 mg) and 26.6% (262 mg), respectively. (a) Isomer a (1) Melting point: 61-62℃ (2) [α] D : +28.1゜ (c0.6, chloroform) (3) 13 C-NMR: 119.0ppm (4) Elemental analysis: Actual value Calculated value (as C 55 H 58 O 11 ) C 74.01% 73.80% H 6.57% 6.53% (b) Isomer b (1) Syrup (2) [α] D : +10.3° (c0.2, Chloroform) (3) 13 C-NMR: 120.4 ppm (4) Elemental analysis: Actual value Calculated value (as C 55 H 58 O 11 ) C 73.92% 73.80% H 6.51% 6.53% Example 5 δ-valerolactone 1 g ( 10.0 mmol) 2,3-di-O-trimethylsilyl ether of
1.07g (2.06mmol) dichloromethane (2ml)
Add TMSOTf20 to the solution at −10 to −20°C under nitrogen flow.
Example 1
The product was worked up in the same manner as above, and the product was separated and purified using a flash column (hexane-ether 5:2) to obtain only the main product in a yield of 40.2%. The other isomer is present in trace amounts, orthoester carbon
The presence of 119.0 ppm was only detectable by 13 C-NMR. Methyl-4,6-di-O-benzyl-2,3-
O-(tetrahydropyran-2-ylidene)-α-
D-mannopyranoside (1) Melting point: 40-41.5℃ (2) [α] D : +44゜ (c0.35, chloroform) (3) 13 C−NMR: 118.5 ppm (4) Elemental analysis: Actual value Calculated value (C 26 H 32 O 7 ) C 68.19% 68.40% H 7.12% 7.07%
Claims (1)
メチルシリル化したジオール類とを、溶液中で、
トリメチルシリルトリフレートを触媒として縮合
させることを特徴とするグリコシリデンアセター
ル類の製造方法。1. In a solution, an aldonic acid lactone with a protected hydroxyl group and a trimethylsilylated diol,
A method for producing glycosylidene acetals, which comprises condensing trimethylsilyl triflate as a catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56051506A JPS57165388A (en) | 1981-04-06 | 1981-04-06 | Preparation of glycosylidene acetal compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56051506A JPS57165388A (en) | 1981-04-06 | 1981-04-06 | Preparation of glycosylidene acetal compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57165388A JPS57165388A (en) | 1982-10-12 |
| JPS6150951B2 true JPS6150951B2 (en) | 1986-11-06 |
Family
ID=12888875
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56051506A Granted JPS57165388A (en) | 1981-04-06 | 1981-04-06 | Preparation of glycosylidene acetal compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57165388A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60174790A (en) * | 1984-02-22 | 1985-09-09 | Toshitsugu Yoshimura | Novel spiro cyclic orthoester compound |
-
1981
- 1981-04-06 JP JP56051506A patent/JPS57165388A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57165388A (en) | 1982-10-12 |
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