Inositol deoxy

An optically inactive isomer, 2-deoxy-myo-inositol (deoxy-scyZZo-inositol) (scylloqneTcitol (7)), m.p. 233-235 , was synthesized by the catalytic reduction of m2/o-inosose-2 in the presence of mineral acid (56) (Fig. 1). Catalytic reduction of inososes or their oximes in mineral acid appears to be a general way for preparing monodeoxyinositols (57a, 6). 

Inosine, 6-benzyloxy-9- -D-ribofuranosyl-2-dimethylamino-hydrogenolysis, 5, 558 Inosine, 2 -deoxy-alkylation, 5, 538 Inosine, 6-phenacylthio-dethiation, S, 559 Inosine 5 -monophosphate biosynthesis, 1, 88 Inosines, thio-synthesis, 5, 584 Inositol, D-l,4-anhydro-synthesis, 1, 416 Inositols synthesis, 1, 416 Insecticides... 

The deoxyinositols (quercitols, cyclohexanepentols) are useful model compounds which display many of the physical and chemical properties of true deoxy sugars. Although (-b)-proto-quercitol, the best known isomer, was isolated from nature 118 years ago, no synthesis has been reported up until now. The synthesis here described is actually that of the (-)-enantiomer, starting with (-)-inositol however, identical procedures applied to the readily available ( + ) or dl-inositol would give (- -) or DL-proto-quercitol, respectively. The natural occurence of, )-proto-quercitol has... 

Deoxy-I,2-0-isopropylidenc-4-C-mcthyl-4-nitro-<-Ajr0-inositol (15) Single Procedure33 ... 

The barium hydroxide catalyzed Henry reaction of 6-deoxy-3-0-methyl-6-nilro-L-ta/r -pyra-nosc (17), generated from l,2-0-isopropylidcnc-3-0-mcthyl-o -D-r/7to-pcntodialdo-1.4-furanose (16), furnishes 5-deoxy-2-GMnethyl-5-nitro-wi o-inositol (18) in 92% yield and 90% purity1 2 3 4 5 6. 

Iyxofuranosyl-( 1 —>2)-1 -[(aminoiminomethyl)amino]-1 -deoxy-D-scy//o-inositol 5-carbamate... 

VlL-l-Deoxy-l-fluoro-myo-inositol (393) and (+)-lD-l-deoxy-l-fluoro-m> oinositol (394) have been prepared from myo-inositol through multi-step reactions involving DAST treatment. 

Selective replacement of hydroxyl groups by bromine has been reported for some inositols and inosamines. DL-2-Amino-2-deoxy-epi-inositol hydrochloride plus acetyl bromide in acetic anhydride gave, after 6 hours at 150°, DL-4-acetamido-l,2,6-tri-0-acetyl-3,5-dibromo-3,4,5-trideoxy-c/uro-inositol in 32% yield, the bromine atoms having been introduced with inversion.407 Under related conditions, DL-epi-... 

This process (also known as the Ferrier II Reaction ) has proved to be of considerable value for the efficient, one-step conversion of 5,6-unsaturated hexopyranose derivatives into functionalized cyclohexanones useful for the preparation of such enantiomerically pure compounds as inositols and their amino, deoxy, unsaturated and selectively O-substituted derivatives, notably phosphate esters. In addition, the products of the carbocyclization have been incorporated into many complex compounds of interest in biological and medicinal chemistry. ... 

The General myo-lnositol and scyllo-Inosamine Pathway. Two distinct cyclitol pathways, which we earlier called Ca (started by myo-inositolphos-phate synthase) and Cb (started by T-deoxy-i cy/to-inosose synthase), are used in the initiation of AGA pathways. Here we will describe the Ca route and the Cb pathway in the paragraph on NEOs (see Section 2.2.2.1.3). The cyclitol pathway in the biosynthetic pathways for STRs, but also for other AGAs such as SPCs, KAS, and FORs and also the mixed type antibiotic HYG-A (see Section 2.2.4.3.1), starts with the formation of myo-inositol in a two-step pathway (Ca) that is not encoded in the itrAtt-clusters. The first step in streptidine biosynthesis (and any other myo-inositol utilising pathway) is the formation of a myo-inositol monophosphate (D-myo-inositol-3-phosphate or L-myo-inositol-1-phosphate) via L-myo-inositol-1-phosphate synthase, which in actinomycetes... 

Formation of the Initial Cyclitol. The first steps of FOR production are the same as in the biosynthesis of STR in short, the first step in FOR biosynthesis is postulated to be the formation of a myo-inositol monophosphate (D-myo-inositol-3-phosphate or L-myo-inositol-1-phosphate) via the cellular l-myo-inositol-1-phosphate synthase as in the STR pathway (Ca pathway see Section 2.2.1.2). As in the itr-Att-clusters, no gene for this enzyme has been found in the/or-cluster. As a second step in FOR biosynthesis the dephosphorylation of D-myo-inositol-3-phosphate via an inositolmonophosphate phosphatase has to follow. A putative gene product with this activity is that of the ForA protein (cf. Tables 2.17 and 2.18). The cyclitol is postulated to be first converted via two enzymes, a cluster-encoded myo-inositol 3-dehydrogenase (ForG member of the GFO/IDH/MocA oxidoreductase family) and the L-glutamine icy//o-3-inosose 3-aminotransferase (ketocyclitol aminotransferase I ForS), to icy//o-inosamine (3-deoxy-3-amino- cy/to-mositol). 

This enzyme [EC 2.1.4.2] catalyzes the reaction of arginine with l-amino-l-deoxy-xcyZ/o-inositol 4-phosphate to produce ornithine and l-guanidino-l-deoxy-scy//o-inositol 4-phosphate. Other substrates include lo-l-gua-nidino-3-amino-l,3-dideoxy-xcy//o-inositol 6-phosphate, streptamine phosphate and 2-deoxystreptamine phosphate. Canavanine can substitute for arginine. 

DPIEL D-3-deoxy-phosphatidyl-fnyo-inositol ether lipid... 

Fig. 3.15. Typical strucutre of a glycosyl phosphatidyl inositol (GPI) anchor. Ins inositol GlcN 2 -amino, 2 -deoxy-glucose Man mannose Etn Ethanolamine, P phosphate.

There are two main points of interest. First, the extent of inversion varied over a wide range, and second, the high degree of inversion found for the aminodeoxy-scyiio- (46) and 3-amino-3-deoxy-chiro-inositol acetates was in marked contrast to the predominant retention of configuration observed in the deamination of simple, equatorial amines. 

Occasionally, a per-O-acetylated amine can be used in the synthesis of a partially acetylated compound. For example, 2-amino-2-deoxy-neo-inositol pentaacetate, which was prepared from hygromycin A, was converted by deamination into 1,2,3,4,6-penta-O-acetyl-myo-inositol.226... 

---