N‐Heterocyclic Carbene‐Catalyzed Benzoin Strategy for Divergent Synthesis of Cyclitol Derivatives from Alditols

Kang, Bubwoong; Sutou, Toshiaki; Wang, Yinli; Kuwano, Satoru; Yamaoka, Yousuke; Takasu, Kiyosei; Yamada, Ken‐ichi

doi:10.1002/adsc.201400712

Cited by 21 publications

(12 citation statements)

References 89 publications

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“…This is possibly ascribable to differences in the preferred conformation of the acylazolium species in the N-phenyl-and N-perfluorophenyl-substituted systems. 56,57 The reaction was extremely slow and produced a negligible amount of R-4f when NHC precursor 1c, bearing a phenyl group with electrondonating groups at its 2,4,6-positions, was used (entry 3). Next, we investigated the effect of the substituent on the indane moiety.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Enhanced Molecular Recognition through Substrate–Additive Complex Formation in N-Heterocyclic-Carbene-Catalyzed Kinetic Resolution of α-Hydroxythioamides

et al. 2022

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We describe a new way of understanding enhanced molecular recognition through substrate–additive complex formation and the development of the first catalytic kinetic resolution of α-hydroxythioamides, which are versatile synthetic building blocks, using chiral N-heterocyclic carbene-catalyzed enantioselective acylation assisted by a carboxylate additive. Mass spectrometry provided evidence for the role of the additive, which forms a hydrogen-bonded complex with α-hydroxythioamide, resulting in both rate and selectivity enhancements. The synthetic applications of the resolved α-hydroxythioamides highlight the usefulness of the developed method.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Enhanced Molecular Recognition through Substrate–Additive Complex Formation in N-Heterocyclic-Carbene-Catalyzed Kinetic Resolution of α-Hydroxythioamides

et al. 2022

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“…Aminocyclitol derivatives are also found to be inhibitors of glycosidases and cell growth . Several strategies, − including chemo-enzymatic approach, SmI 2 -mediated pinacol-type coupling, and intramolecular NHC-catalyzed benzoin-type condensation, are available for the construction of aminocyclitol frameworks. Interestingly, McMurry coupling of a suitably substituted acyclic dialdehyde, wherein carbocyclization accompanied by installation of two of the hydroxyl groups of aminocyclitols, has never been investigated.…”

Section: Introductionmentioning

confidence: 99%

A Chiron Approach to Diversity-Oriented Synthesis of Aminocyclitols, (−)-Conduramine F-4 and Polyhydroxyaminoazepanes from a Common Precursor

Harit

Ramesh

2016

J. Org. Chem.

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The total syntheses of aminocyclitols, (-)-conduramine F-4, and polyhydroxyaminoazepanes have been achieved from a common precursor derived from tri-O-benzyl-d-glucal through a 'diversity-oriented' approach. Tri-O-benzyl-d-glucal was converted into a protected 1,6-diol through a sequence of steps that include transformation to a 2-tosylamidoglucose derivative, selective deprotection of primary C-6 benzyloxy group, LiAlH-mediated one-step reduction of acetate groups, and reductive ring opening of the resulting hemiacetal as the key steps. The 1,6-diol served as a common precursor in our diversity oriented approach toward the target molecules. Mesylation of the diol followed by double nucleophilic substitution reaction with primary amines led to the synthesis of amino-substituted polyhydroxyazepanes. On the other hand, dialdehyde obtained from the oxidation of 1,6-diol was found to be a convenient starting material for the synthesis of aminocyclitols and (-)-conduramine F-4. McMurry coupling of the dialdehyde was successfully employed, for the first time, to construct the carbocyclic framework of aminoyclitols, while bis-Wittig olefination of the dialdehyde followed by Grubb's(II)-catalyzed RCM delivered (-)-conduramine F-4. The stereochemistry of newly created chiral centers in aminocyclitols was established through single crystal X-ray crystallography and detailed NOE studies.

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“…The use of these readily available chiral pool-derived substrates can also lead to diastereofacial selectivity during C–C bond formation. It is worth noting that very few examples of diastereoselective benzoin reactions have been reported …”

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confidence: 99%

Chemo- and Diastereoselective N-Heterocyclic Carbene-Catalyzed Cross-Benzoin Reactions Using N-Boc-α-amino Aldehydes

Haghshenas

Gravel

2016

Org. Lett.

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N-Boc-α-amino aldehydes are shown to be excellent partners in cross-benzoin reactions with aliphatic or heteroaromatic aldehydes. The chemoselectivity of the reaction and the facial selectivity on the amino aldehyde allow cross-benzoin products to be obtained in good yields and good diastereomeric ratios. The developed method is utilized as the key step in a concise total synthesis of d-arabino-phytosphingosine.

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N‐Heterocyclic Carbene‐Catalyzed Benzoin Strategy for Divergent Synthesis of Cyclitol Derivatives from Alditols

Cited by 21 publications

References 89 publications

Enhanced Molecular Recognition through Substrate–Additive Complex Formation in N-Heterocyclic-Carbene-Catalyzed Kinetic Resolution of α-Hydroxythioamides

Enhanced Molecular Recognition through Substrate–Additive Complex Formation in N-Heterocyclic-Carbene-Catalyzed Kinetic Resolution of α-Hydroxythioamides

A Chiron Approach to Diversity-Oriented Synthesis of Aminocyclitols, (−)-Conduramine F-4 and Polyhydroxyaminoazepanes from a Common Precursor

Chemo- and Diastereoselective N-Heterocyclic Carbene-Catalyzed Cross-Benzoin Reactions Using N-Boc-α-amino Aldehydes

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