Allyloxy and Propargyloxy Group Migration: Role of Remote Group Participation in the Synthesis of 5-C-Nucleosides and Other Sugar Derivatives

Mukherjee, Subhrangshu; Tripathi, Prem Prakash; Mandal, Sukhendu

doi:10.1021/ol301851q

Cited by 9 publications

(1 citation statement)

References 29 publications

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“…in some cases. [110][111][112] Our studies of reactions of alkoxy-substituted acetals showed that the presence of an alkoxy group, which is inductively electron-withdrawing, can accelerate acetal hydrolysis if it can approach the developing carbocationic carbon atom (Scheme 54). 113,114 The rate acceleration trends in hydrolysis were also observed for solvolysis of tosylates (Scheme 55).…”

Section: Account Synlettmentioning

confidence: 99%

Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs Selectivity, and Neighboring-Group Participation

Woerpel,

Chun,

Luu

2024

Synlett

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Acetal substitution reactions can proceed by a number of mechanisms, but oxocarbenium ion intermediates are involved in many of these reactions. Our research has focused on understanding the conformational preferences, structures, and reactions of these intermediates. This account summarizes our observations that electrostatic effects play a significant role in defining the preferred conformations, and that torsional effects determine how those intermediates react. Neighboring-group effects are not as straightforward as they might seem, considering that oxocarbenium ion intermediates are in equilibrium with structures that involve stabilization by a nearby substituent.1 Introduction2 Unexpected Stereoselectivities3 Determining Conformational Preferences of Oxocarbenium Ions4 Structures of Carbocations by NMR Spectroscopy and X-ray Crystallography5 Stereoelectronic Models for Reactions Involving Other Oxocarbenium Ions6 Stereoselectivity and Reactivity: When They Correlate, When They Do Not7 Neighboring–Group Participation Is Not as Simple as It Seems8 What Is True for Carbocations Is True for Carbonyl Compounds9 Stereoelectronic and Torsional Effects in Reactions of Enolates10 Summary of Expected Selectivities for Reactions of Cyclic Acetals11 Conclusion

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Section: Account Synlettmentioning

confidence: 99%

Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs Selectivity, and Neighboring-Group Participation

Woerpel,

Chun,

Luu

2024

Synlett

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Debenzylative Cycloetherification: An Overlooked Key Strategy for Complex Tetrahydrofuran Synthesis

Tikad

Delbrouck

Vincent

2016

Chemistry A European J

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Tetrahydrofuran (THF) is a major structural feature found in many synthetic and natural products displaying a variety of biological properties. This review summarizes the main synthetic approaches that have been developed to construct tetrahydrofuran moieties involving debenzylative cycloetherification reactions (DBCE). Interestingly, this reaction is regio- and stereoselective without the requirement of a selective protection/deprotection strategy. Many applications of this process have been reported, including carbafuranoside synthesis, regioselective deprotection of the benzyl group positioned γ to an alkene, and total synthesis of natural products. The stereochemical outcome and the mechanism of these interesting transformations are also discussed.

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Gold(I)‐Catalyzed Cycloisomerization of ortho‐(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings

Fang

Wei

Tang

et al. 2017

Chemistry A European J

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Gold(I)-catalyzed cycloisomerization of ortho-(propargyloxy)arenemethylenecyclopropanes afforded two different types of products, that is, products of methylenecyclopropane migration and cycloisomerization products of the methylenecyclopropane moiety, controlled jointly by electronic and steric effects of the adjacent substituents. Furthermore, the corresponding cycloisomerization products could be also produced in an enantiomerically enriched manner.

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Allyloxy and Propargyloxy Group Migration: Role of Remote Group Participation in the Synthesis of 5-C-Nucleosides and Other Sugar Derivatives

Cited by 9 publications

References 29 publications

Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs Selectivity, and Neighboring-Group Participation

Acetal Substitution Reactions: Stereoelectronic Effects, Conformational Analysis, Reactivity vs Selectivity, and Neighboring-Group Participation

Debenzylative Cycloetherification: An Overlooked Key Strategy for Complex Tetrahydrofuran Synthesis

Gold(I)‐Catalyzed Cycloisomerization of ortho‐(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings

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