The use of Grignard reagents in the synthesis of carbohydrates. I. The synthesis of deoxy and branched-chain deoxy sugars.
スポンサーリンク
概要
- 論文の詳細を見る
Two branched-chain deoxy sugars, methyl 5,6-<I>O</I>-cyclohexylidene-3-deoxy-2-<I>C</I>-methyl-β-D-<I>arabino</I>-hexofuranoside and its α-D-<I>ribo</I> isomer, were easily prepared by the one-step reaction of methyl 5,6-<I>O</I>-cyclohexylidene-3-<I>O</I>-mesyl-β-D-allofuranoside (<B>3a</B>) with methylmagnesium iodide. Similarly, the corresponding α-mesylate (<B>4a</B>) gave methyl 5,6-<I>O</I>-cyclohexylidene-3-deoxy-2-<I>C</I>-methyl-α-D-<I>ribo</I>-hexofuranoside. It was demonstrated that these reactions involved 1,2-hydride shifts. The reaction of <B>3a</B> and <B>4a</B> with <I>t</I>-butylmagnesium bromide yielded two deoxy sugars, methyl 5,6-<I>O</I>-cyclohexylidene-3-deoxy-β-D-<I>arabino</I>-hexofuranoside and the corresponding α-D-<I>ribo</I> isomer, respectively. Under certain reaction conditions with the Grignard reagents, the sulfonate (<B>3a</B>) afforded dimeric compounds, in which two furanose rings were directly bound with a carbon–carbon bond. A convenient method for the preparation of the sulfonates (<B>3a</B> and <B>4a</B>) is also reported.
- 公益社団法人 日本化学会の論文
著者
-
Emoto Sakae
The Institute of Physical and Chemical Research
-
Kawana Masajiro
The Institute of Physical and Chemical Research
関連論文
- Catalytic activities of salicylaldehyde derivatives. V. Syntheses and catalytic activities of some trimethylammonio derivatives of salicylaldehyde in the racemization of L-glutamic acid.
- The use of Grignard reagents in the synthesis of carbohydrates. I. The synthesis of deoxy and branched-chain deoxy sugars.
- The use of Grignard reagents in the synthesis of carbohydrates. III. The one-way anomerization of methyl glycofuranosides and the opening of their furanose rings.
- Catalytic Activities of Salicylaldehyde Derivatives. III. An Improved Synthesis of 6-Nitrosalicylaldehyde
- Pyridoxal model compounds. II. The Diels-Alder reaction of 9-substituted 2-methoxyanthracenes.
- Formation and Reduction of 2-Acyl-1-tetralones
- The Reaction of Several o-Methoxy Aromatic Aldehydes with Ethylthioxide. Novel Substitution and Condensation
- Catalytic activities of salicylaldehyde derivatives. VII. Synthesis and catalytic activity of (2-formyl-3-hydroxyphenyl)dimethylsulfonium salt in the racemization of L-glutamic acid.
- Aldol condensation of aldehydes with ketones promoted by the copper(II) ion. Orientation to the chemical model for metalloaldolases.
- Pyridoxal Model Compounds. I. The Regioselective Formylation of Methoxy-substituted Aromatic Compounds
- Asymmetric Synthesis with Sugar Derivatives. V. The Synthesis of α-Hydroxy Acids on Insoluble Polymer Supports