29267-04-7Relevant articles and documents
Useful access to enantiomerically pure protected inositols from carbohydrates: The aldohexos-5-uloses route
D'Andrea, Felicia,Catelani, Giorgio,Guazzelli, Lorenzo,Pistarà, Venerando
, p. 2343 - 2350 (2016/11/17)
The intramolecular aldol condensation of aldohexos-5-ulose derivatives of the D-xylo and L-ribo stereoseries has been studied. Only one of the four possible inososes was isolated from both stereoseries in reasonable yields (30-38%). The results obtained, together with the previous findings for the L-arabino and L-lyxo stereoseries, allowed for the rationalisation of a mechanism of the reaction based on open-transition-state models and electron-withdrawing inductive effects. Complementary reductions of the intermediate inososes were possible by changing the reaction conditions, and two isomeric inositol derivatives were obtained with complete stereoselection from each inosose. The presented approach permits us to control the configuration of three out of the six stereocentres of the inositol frame and gives access to seven of the nine inositols. Noteworthy, for the D-xylo derivative, the two-step sequence (condensation followed by reduction with NaBH(OAc)3) represents the biomimetic synthesis of myo-inositol. Furthermore, the sugar-based pathway leads directly to enantiomerically pure selectively protected inositols and does not require any desymmetrisation procedure which is needed when myo-inositol and other achiral precursors are employed as starting materials. As an example of application of the method, the indirect selective protection of secondary inositols' hydroxy functions, by placing specific protecting groups on the aldohexos-5-ulose precursor has been presented.
Orthogonally protected cyclohexanehexols by a "one reaction - One product" approach: Efficient access to cyclitols and their analogs
Jagdhane, Rajendra C.,Shashidhar, Mysore S.
supporting information; experimental part, p. 2945 - 2953 (2010/08/07)
Differentially protected myo-inositol derivatives were prepared from commercially available myo-inositol through regioselective O-alkylation reactions, which give a single product in each step. These derivatives were converted into six isomeric inositol derivatives carrying orthogonal hydroxy protecting groups. For all these reactions, conditions were chosen to prevent the formation of isomeric products, which obviates the need for separation of isomers and provides the required cyclitol derivative in very good yields. The synthetic potential of these derivatives was illustrated by the conversion of some of the orthogonally protected inositol derivatives into other cyclitol derivatives. Isomeric inositols were also prepared by the global deprotection of all the hydroxy groups.
Synthesis of enantiopure cyclitols from (±)-3-bromocyclohexene mediated by intramolecular oxyselenenylation employing (S,S)-hydrobenzoin and (S)-mandelic acid as chiral sources
Lee, Yong Joo,Lee, Kyunghoon,Jung, Sea Ill,Jeon, Heung Bae,Kim, Kwan Soo
, p. 1987 - 2001 (2007/10/03)
Reaction of 3-bromocyclohexene with (S,S)-hydrobenzoin and (S)-mandelic acid and subsequent intramolecular oxyselenenylation of the resulting allylic ethers followed by oxidation-elimination afforded the valuable cis-fused bicyclic olefins, (1S,3S,4S,6R)-3,4-diphenylbicyclo[4,4,0]-2,5-dioxa-7-decene and (1S,3S,4R)-3-phenyl-4a,7,8,8a-tetrahydro-benzo[1,4]dioxan-2-one, respectively. Further stereoselective transformation of these cis-fused bicyclic olefins afforded the enantiopure cyclohexitols, muco-quercitol, D-chiro-inocitol and allo-inocitol.
Intramolecular aldol cyclization of L-lyxo-hexos-5-ulose derivatives: A new diastereoselective synthesis of D-chiro-inositol
Catelani, Giorgio,Corsaro, Antonino,D'Andrea, Felicia,Mariani, Manuela,Pistarà, Venerando
, p. 3313 - 3315 (2007/10/03)
The DBU-promoted intramolecular aldol condensation of two partially protected L-lyxo-hexos-5-ulose derivatives (8 and 9), in turn obtained starting from methyl β-D-galactopyranoside, takes place with fairly good yield and complete diastereoselectivity to
A norbornyl route to cyclohexitols: Stereoselective synthesis of conduritol-E, allo-inositol, MK 7607 and gabosines
Mehta, Goverdhan,Lakshminath, Sripada
, p. 3509 - 3512 (2007/10/03)
A novel fragmentation sequence within the norbornane system, involving C1-C7 bond scission, provides convenient access to a highly functionalized and versatile cyclohexenoid building block which has been further elaborated to a range of cyclohexitols such as, conduritol E, allo-inositol and gabosine B. Our synthesis of the structure corresponding to gabosine K indicates that the structure of this natural product needs to be revised. (C) 2000 Elsevier Science Ltd.
Stereochemical observations on the bromate induced monobromopentahydroxylation of benzene by catalytic photoinduced charge transfer osmylation. A concise synthesis of (±)-pinitol
Jung, Pierre M. J.,Motherwell, William B.,Williams, Alvin S.
, p. 1283 - 1284 (2007/10/03)
The use of lower temperatures in the title reaction favours the formation of the neo diastereoisomer of the deoxybromoinositol whose diisopropylidene derivative can be converted in three steps to (±)-pinitol.
Katalytische, photoinduzierte Charge-Transfer-Osmylierung, ein neuer Weg von Arenen zu Cyclitderivaten
Motherwell, William B.,Williams, Alvin S.
, p. 2207 - 2209 (2007/10/03)
Keywords: Aren-Oxidation; Charge-Transfer; Condurite; Inosite; Osmylierung
Catalytic One-Pot Osmylation of Cyclohexadienes: Stereochemical and Conformational Studies of the Resulting Polyols
Tschamber, Theophile,Backenstrass, Frederique,Fritz, Hans,Streith, Jacques
, p. 1052 - 1060 (2007/10/02)
Catalytic double osmylation is described for a series of cyclohexadienes in acetone/H2O in the presence of the co-oxidant N-methylmorpholine N-oxide (NMO).The formation of polyols occurred stereospecifically with cyclohexadienes 3, 7, and 11a, leading thereby to tetrols 5a, and 9a and to allo-inositol (14a), respectively.To the contrary, trans-cyclohexadiene-diol 15a gave a mixture of the stereoisomeric inositols 18a (epi), 19a (neo), and 20a (chiro).High-field NMR let to clearcut conformational analyses of the polyhydroxylated derivatives.
