Evidence for cyclic bromonium ion transfer in electrophilic bromination of alkenes: Reaction of ω-alkenyl glycosides with aqueous N-bromosuccinimide

Rodebaugh, Robert; Fraser‐Reid, Bert

doi:10.1016/s0040-4020(96)00349-3

Cited by 53 publications

(31 citation statements)

References 26 publications

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“…This caused precipitation of the starting material, which was removed by filtration; the resulting filtrate was concentrated to yield a mixture of the products. The 1 H-NMR spectroscopic data of 1-allyl-2,3,4,6-tetra-O-benzyl-α-D-glucopyranoside [31] and 1-allyl-2,3,4,6-tetra-Obenzyl-β-D-glucopyranoside [32] were in agreement with the data found in literature. …”

Section: -Allyl-2346-tetra-o-benzyl-α-d-glucopyranoside and 1-allsupporting

confidence: 89%

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Scope of the allylation reaction with [RuCp(PP)]⁺ catalysts: changing the nucleophile or allylic alcohol

Rijn

Guijt

Vries

et al. 2010

Applied Organom Chemis

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The scope of the dehydrative allylation reaction using allyl alcohol as allyl donor with [RuCp(PP)] + complexes as catalysts is explored. Aliphatic alcohols are successfully allylated with allyl alcohol or diallyl ether, obtaining high selectivity for the alkyl allyl ether. The reactivity of aliphatic alcohols is in the order of primary > secondary >> tertiary. The tertiary alcohol 1-adamantanol reacts extremely slowly in the absence of strong acid, but when HOTs is added, reasonable yields of 1-adamantyl allyl ether are obtained. The alkyl allyl ether is found to be the thermodynamically favored product over diallyl ether. Apart from alcohols, thiols and indole are also efficiently allylated, while aniline acts as a catalyst inhibitor. Allylation reactions with various substituted allylic alcohols give products with retention of the substitution pattern. It is proposed that a Ru(IV) σ -allyl species plays a key role in the mechanism of these allylation reactions.

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Section: -Allyl-2346-tetra-o-benzyl-α-d-glucopyranoside and 1-allsupporting

confidence: 89%

“…An α to β ratio of 1 : 3.5 (Scheme 4) was found as deduced from the 1 H-NMR spectra. [31,32] The preference for the less hindered β-product was most likely induced by the relatively crowded catalyst.…”

Section: Allylation Reactions Of Alcohols With Allyl Alcohol As the Amentioning

confidence: 99%

Scope of the allylation reaction with [RuCp(PP)]⁺ catalysts: changing the nucleophile or allylic alcohol

Rijn

Guijt

Vries

et al. 2010

Applied Organom Chemis

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“…1 The antecedents of epoxidation of allyl glycosides of peracetylated sugars show that this reaction takes place with very scarce or no diastereoselectivity. 17,18 At the same time, when the reaction is carried out on substrates with unprotected OH on C-2, the diastereomeric excess is considerable (80%), the major part having R-configuration. This suggests the formation of a hydrogen bond between the OH group and the peroxyacid, preferentially stabilizing the transition state related to the electrophilic addition to the Re-face of the double bond.…”

Section: Resultsmentioning

confidence: 99%

Alkylating agents from sugars: Synthesis of chlorambucil derivatives carried by chiral glycosyl glycerols derived from D‐Glucosamine

et al. 2002

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Chlorambucilamide derivatives involving chiral glycosyl glycerols derived from D-glucosamine were synthesized in good yield by coupling the chlorambucil moiety to the amino group of omega-amino-(omega-1)-hydroxyalkyl 2-acylamino-4,6-O-benzylidene-2-deoxy-beta-D-glucopyranosides, and subsequent hydrolysis of the benzylidene group. The starting material was easily available from 2-acetamido-2-deoxy-D-glucose. The bonding of 2,3,4,6-tetra-O-pivaloyl-beta-D-galactopyranosylamine to chlorambucil by formation of an amide function is also described.

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“…Although both faces of the pendant alkene are accessible to produce two diastereomeric bromonium species, only one (less hindered) oxonium intermediate was apparently selectively transformed into the product, presumably owing to facile bromonium transfer between alkenes and reversible oxonium formation (Figure 6). [79] To avoid steric hindrance, the exo -orientation of the bromo side chain of the oxonium intermediate is preferred. In this chemistry, as in many other bromocyclizations (see below), BDSB proved superior to other commonly used bromonium sources.…”

Section: Stereoselective Halogenation Methods and Applications In mentioning

confidence: 99%

Stereoselective Halogenation in Natural Product Synthesis

2016

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At last count, nearly 5000 halogenated natural products have been discovered. In approximately half of these compounds, the carbon atom to which the halogen is bound is sp3‐hybridized; therefore, there are an enormous number of natural products for which stereocontrolled halogenation must be a critical component of any synthesis strategy. In this Review, we critically discuss the methods and strategies used for stereoselective introduction of halogen atoms in the context of natural product synthesis. Using the successes of the past, we also attempt to identify gaps in our synthesis technology that would aid the synthesis of halogenated natural products, as well as existing methods that have not yet seen application in complex molecule synthesis. The chemistry described herein demonstrates yet again how natural products continue to provide the inspiration for critical advances in chemical synthesis.

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Evidence for cyclic bromonium ion transfer in electrophilic bromination of alkenes: Reaction of ω-alkenyl glycosides with aqueous N-bromosuccinimide

Cited by 53 publications

References 26 publications

Scope of the allylation reaction with [RuCp(PP)]⁺ catalysts: changing the nucleophile or allylic alcohol

Scope of the allylation reaction with [RuCp(PP)]⁺ catalysts: changing the nucleophile or allylic alcohol

Alkylating agents from sugars: Synthesis of chlorambucil derivatives carried by chiral glycosyl glycerols derived from D‐Glucosamine

Stereoselective Halogenation in Natural Product Synthesis

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Evidence for cyclic bromonium ion transfer in electrophilic bromination of alkenes: Reaction of ω-alkenyl glycosides with aqueous N-bromosuccinimide

Cited by 53 publications

References 26 publications

Scope of the allylation reaction with [RuCp(PP)]+ catalysts: changing the nucleophile or allylic alcohol

Scope of the allylation reaction with [RuCp(PP)]+ catalysts: changing the nucleophile or allylic alcohol

Alkylating agents from sugars: Synthesis of chlorambucil derivatives carried by chiral glycosyl glycerols derived from D‐Glucosamine

Stereoselective Halogenation in Natural Product Synthesis

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Product

Resources

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Scope of the allylation reaction with [RuCp(PP)]⁺ catalysts: changing the nucleophile or allylic alcohol

Scope of the allylation reaction with [RuCp(PP)]⁺ catalysts: changing the nucleophile or allylic alcohol