Efficient and enantiodivergent synthesis of (+)- and (-)-pinitol

Hudlický, Tomáš; Price, John D.; Fan, Rulin; Tsunoda, Toshiya

doi:10.1021/ja00181a081

Cited by 152 publications

(55 citation statements)

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“…During the course of another project, we had occasion to convert the cis-1,2-dihydrocatechol 1a, via the corresponding acetonide 4a [3] (Scheme 1), into the previously reported and well-known epoxide 5a. [3] A 'streamlined' procedure for doing so is described in the Experimental section and this allowed us to acquire compound 5a in 93 % yield on a multi-gram scale.…”

Section: Resultsmentioning

confidence: 99%

“…[3] A 'streamlined' procedure for doing so is described in the Experimental section and this allowed us to acquire compound 5a in 93 % yield on a multi-gram scale. This epoxide was treated with the anion derived from p-methoxybenzyl alcohol (p-MBOH) under the expectation [4] that the nucleophilic ring-opening product 6a would form and then, from it, the corresponding ether upon quenching with methoxymethyl chloride (MOMCl).…”

Section: Resultsmentioning

confidence: 99%

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New, Homochiral Synthons Obtained through Simple Manipulations of Enzymatically Derived 3-Halo-cis-1,2-dihydrocatechols

et al. 2015

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The bromoepoxide 5a, which is obtained from the homochiral and enzymatically derived cis-1,2-dihydrocatechol 1a, is readily and efficiently transformed into either isomer 8a or the corresponding methoxymethyl-ether 2a. Though both of these products can be fully characterized, they are somewhat unstable, with the former being converted into the crystalline enone 3a on standing and the latter readily participating in a Diels-Alder cycloaddition reaction with the potent dienophile N-phenyl-1,2,4-triazoline-3,5-dione to give adduct 7a. The single-crystal X-ray structures of compounds 3a and 7a are reported. Using the related chemistry the chloro-analogue, 3b, of enone 3a can be obtained.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

New, Homochiral Synthons Obtained through Simple Manipulations of Enzymatically Derived 3-Halo-cis-1,2-dihydrocatechols

et al. 2015

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“…While several differentially protected 8 chiro-inositols have been synthesized, [9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] we sought a general strategy for the syntheses of a complete set of penta-O-benzyl-D D-chiro-inositols, each with a different unprotected hydroxyl group for glycosylation. Since chiro-inositol has a C 2 axis of symmetry, the set consists of only three different penta-O-benzyl-chiro-inositols: 8, 9, and 10.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of galactosaminyl d-chiro-inositols

Marnera

d’Alarcao

2006

Carbohydrate Research

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“…Protection of 1 followed by epoxidation leads to the previously described epoxide 2. 13 The vinyl bromide is then dehalogenated to afford olefin 12. Previous reports have described the failure to carry out this transformation under similar conditions.…”

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The chiro-Inositols and Related Cyclitols as Chiral Monomers for Polymerization: Expansion of a Family of Chiral Polymers

Trant

Hudlický

2014

Synlett

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Three different synthetic approaches to three different classes of oligomeric and polymeric inositol and inositol-like derivatives are presented: Grubbs cross-metathesis polymerization, Lewis acid catalyzed epoxide opening, and head-to-tail Diels-Alder polymerization. All three approaches lead to the formation of oligomers and polymers. The oligomers/polymers formed range from three (low-molecular-weight fraction of Diels-Alder polymerization) to 60 (Lewis acid catalyzed polymerization) repeats of inositol or inositol-like units. The molecular weights of the polymers were characterized by gel-permeation chromatography (GPC), MALDI, and NMR end-group analysis.Chiral polymers are of great interest for diverse applications including their use as stationary phases for the separation of enantiomers 1 or as heterogeneous and easily recoverable ligands or catalysts. 2 The complex, varied, chiral, and highly hydroxylated structure of carbohydrates makes oligosaccharides one of the most useful naturally occurring polymers for these purposes, but the lability of the glycosidic linkage somewhat limits their use in the presence of harsh conditions. An isosteric, but more stable, alternative to the monosaccharides would be the inositols; however, it is more difficult to generate polymers of this class because of the lack of a clear chemoselective differentiation of the hydroxyl groups. The de novo preparation of functionalized polyhydroxycyclohexanes is available by the whole cell fermentation of arenes, such as bromobenzene, with E. coli JM109 (pDTG601A) strain that overexpresses the enzyme toluene dioxygenase. This protocol allows for subsequent selective introduction of the remaining functionalities in the homochiral monomers prior to their polymerization. We would like to report a series of recent efforts in our laboratory towards the preparation of chiral polymers based on D-or L-chiro-inositol and simple tetrahydroxylated derivatives. We have previously reported the synthesis and preparation of several well-defined inositol oligomers, 3 and a bisbutenyl ether of polymer of D-chiro-inositol. 4 Three different approaches and polymeric structures are presented to demonstrate the chemical and structural versatility of these building blocks: a Grubbs metathesis approach providing chiral inositols connected through a carbon-chain linker; an aluminum-catalyzed epoxide opening approach leading to polymers of oxygen substituted cyclohexene oxides lacking spacers between the cyclitols; and a head-to-tail Diels-Alder polymerization of functionalized inositols generating cyclohexene spacers between the repeating monomers. A general method of synthesis for conduritols 5 and inositols, 6 including their fluorinated 7 and isotopically 8 labeled derivatives, has been developed previously in our laboratory and have been extensively reviewed. 9 Mono-or disubstituted benzene rings are enantioselectively cis-dihydroxylated by toluene dioxygenase, providing the required functionality for elaboration into conduritols, inositols, pseudosugars...

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Efficient and enantiodivergent synthesis of (+)- and (-)-pinitol

Cited by 152 publications

References 0 publications

New, Homochiral Synthons Obtained through Simple Manipulations of Enzymatically Derived 3-Halo-cis-1,2-dihydrocatechols

New, Homochiral Synthons Obtained through Simple Manipulations of Enzymatically Derived 3-Halo-cis-1,2-dihydrocatechols

Synthesis of galactosaminyl d-chiro-inositols

The chiro-Inositols and Related Cyclitols as Chiral Monomers for Polymerization: Expansion of a Family of Chiral Polymers

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