Journal of the Chemical Society. Perkin transactions I p. 1717 - 1727 (1996)
Update date:2022-08-03
Topics:
Lampe, Dethard
Liu, Changsheng
Mahon, Mary F.
Potter, Barry V. L.
Routes for the synthesis of scyllo-inositol tris- and tetrakis-phosphates and 2-deoxy-2-fluoro-myo-inositol 1,4,5-trisphosphate from myo-inositol have been devised. For DL-scyllo-inositol 1,2,4-trisphosphate, DL-1-O-allyl-3,6-di-O-benzyl-4-5-O-isopropylidene-scyllo-inositol was prepared from the triflate of DL-1-O-allyl-3,6-di-O-benzyl-4,5-O-isopropylidene-myo-inositol by inversion at C-2. Removal of the isopropylidene group and phosphorylation gave the protected trisphosphate. Deblocking with sodium in liquid ammonia afforded racemic scyllo-inositol 1,2,4-trisphosphate. DL-1-O-Allyl-3,6-di-O-benzyl-4,5-O-isopropylidene-scyllo-inositol was resolved into its enantiomers by means of the crystalline 2-O-camphanate ester. The structure of one diastereoisomer, 1D-O-allyl-3,6-di-O-benzyl-2-O-[( - )-camphanoyl]-4,5-O-isopropylidene-scyllo-inositol was determined by single-crystal X-ray crystallography. 1D-( + )-1-O-Allyl-3,6-di-O-benzyl-4,5-O-isopropylidene-scyllo-inositol was used to prepare 1L-( - )-scyllo-inositol 1,2,4-trisphosphate in a fashion analogous to the racemic modification. DL-1-O-Allyl-3,6-di-O-benzyl-scyllo-inositol was isomerised to the (Z)-prop-1-enyl derivative. The propenyl group was then removed to give the meso-1,4-di-O-benzyl-scyllo-inositol. Phosphitylation followed by oxidation or sulfoxidation gave the fully protected tetrakis-phosphate or -phosphorothioate, respectively. After deblocking and purification, scyllo-inositol 1,2,4,5-tetrakisphosphate and scyllo-inositol 1,2,4,5-tetrakisphosphorothioate were obtained. DL-1-O-Allyl-3,6-di-O-benzyl-4,5-O-isopropylidene-scyllo-inositol was isomerised to the 1-O-[(Z)-prop-1-enyl] derivative which was converted into the 2-0-triflate. Displacement of the triflate using tetrabutylammonium fluoride proceeded with inversion of configuration to give DL-3,6-di-O-benzyl-2-deoxy-2-fluoro-4,5-O-isopropylidene-1-O-([(Z)-prop-1-enyl]- myo-inositol. Removal of propenyl and isopropylidene groups afforded DL-3,6-di-O-benzyl-2-deoxy-2-fluoro-myo-inositol, which was phosphitylated and the product oxidised to give the fully protected 2-fluoro trisphosphate. Deprotection furnished DL-2-deoxy-2-fluoro-myo-inositol 1,4,5-trisphosphate. These compounds will be useful probes for investigation of the polyphosphoinositide pathway of cellular signalling.
View MoreYancheng Smiling Imp & Exp Co., Ltd.
Contact:+86-515-83173586
Address:Rm1207, BLD#03, Phoenix Plaza, Juheng Road, Yancheng, Jiangsu, P.R. China
Jiaxing Carry Bio-Chem Technology Co.,Ltd
website:http://www.carrybiotech.com
Contact:0573-82788958
Address:Add.Fl 3th, Pharm Vally,Kaichuang Rd, Xiuzhou District, Jiaxing, Zhejiang,314031,China
website:http://www.eastarchem.com/
Contact:1-800-898-2436
Address:1215 K Street, STE 1700
Hefei EnliPharma Tecnology Co.,Ltd
Contact:0086-551-66399836
Address:Qing Cheng ShuiXiang Building 805, Mengcheng North Road , ShuangFeng Economic Development Zone Anhui HeFei
Refine Chemicals Science & Technology Technology Developing Co., Ltd.
Contact:+86-22-87899130
Address:No.12,west keyan road,Tianjin City
Doi:10.1016/j.tetlet.2003.11.086
(2004)Doi:10.1016/j.tetlet.2006.06.060
(2006)Doi:10.1039/b316633c
(2004)Doi:10.1002/anie.200353043
(2004)Doi:10.1016/S0040-4039(03)01361-3
(2003)Doi:10.1021/jo01326a001
(1979)