Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

Soltanzadeh, Bardia; Jaganathan, Arvind; Staples, Richard J.; Borhan, Babak

doi:10.1002/anie.201502341

Cited by 55 publications

(24 citation statements)

References 76 publications

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“…Our recent mechanistic work, 10 stemming from our ongoing interest in developing asymmetric halofunctionalization reactions, 11 reaffirms the incompleteness of the elementary textbook picture, calling for inclusion of a concerted Ad E 3-type path (formally Ad E 2 for these halocyclizations, where the nucleophile is intramolecular; see Figure 1, path C) 12 in which electrophilic attack on the olefin is activated by the nucleophilic partner's simultaneous electron donation. The present study explores how two species, alkenes and nucleophiles, which otherwise might be expected to electronically repel each other, interact to enable the attack of an approaching electrophile.…”

Section: Introductionmentioning

confidence: 85%

Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent

et al. 2016

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Emerging work on organocatalytic enantioselective halocyclizations naturally draws on conditions where both new bonds must be formed under delicate control, the reaction regime where the concerted nature of the AdE3 mechanism is of greatest importance. Without assistance, many simple alkene substrates react slowly or not at all with conventional halenium donors under synthetically relevant reaction conditions. As demonstrated earlier by Shilov, Cambie, Williams, Fahey, and others, alkenes can undergo a concerted AdE3-type reaction via nucleophile participation, which sets the configuration of the newly created stereocenters at both ends in one step. Herein, we explore the modulation of alkene reactivity and halocyclization rates by nucleophile proximity and basicity, through detailed analyses of starting material spectroscopy, addition stereopreferences, isotope effects, and nucleophile–alkene interactions, all obtained in a context directly relevant to synthesis reaction conditions. The findings build on the prior work by highlighting the reactivity spectrum of halocyclizations from stepwise to concerted, and suggest strategies for design of new reactions. Alkene reactivity is seen to span the range from the often overgeneralized “sophomore textbook” image of stepwise electrophilic attack on the alkene and subsequent nucleophilic bond formation, to the nucleophile-assisted alkene activation (NAAA) cases where electron donation from the nucleophilic addition partner activates the alkene for electrophilic attack. By highlighting the factors that control reactivity across this range, this study suggests opportunities to explain and control stereo-, regio-, and organocatalytic chemistry in this important class of alkene additions.

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Section: Introductionmentioning

confidence: 85%

Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent

et al. 2016

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“…[5] Consequently,v arious synthetic methods have been developed to access an oxazoline core. [6] However, there have been only af ew scattered reports on the formationo f2imino-1,3-oxazolines, whicha re regardeda st he precursorso f oxazolones, widely existing in an umber of natural products and pharmacological activec ompounds. [7] Condensationo fahaloketones and symmetrical diarylureas in the presence of bromine gives 2-aryl-imino-3-aryl-1,3-oxazolines.…”

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confidence: 99%

PIDA‐Mediated Formal Olefinic C=C Bond Cleavage of α‐Oxo‐Ketene N,N‐Acetals toward Substituted Oxazolines

Guo

Huang

Jiang

et al. 2018

Chemistry A European J

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The hypervalent iodine reagent PhI(OAc) (PIDA) mediated the formal oxidative C=C bond cleavage and subsequent cyclization of internal olefins, that is, α-oxo-ketene N,N-acetals, which afforded substituted oxazolines. Isothiazoline derivatives were obtained from the reactions of α-thioxo-ketene N,N-acetals with PIDA under the same conditions. Hydrolysis of the resultant oxazoline derivatives led to highly functionalized oxazolones. A plausible mechanism was proposed based upon the formation of isothiazoline-type intermediates.

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“…In the paper, two examples of styrene derivatives were examined to give the products in moderate enantiomeric excesses. In 2015, Borhan also reported the haloesterification of allylic amides using (DHQD) 2 PHAL as catalyst . However, no successful example of catalytic asymmetric haloesterification of non‐functionalized simple alkenes has been reported.…”

Section: Figurementioning

confidence: 99%

Catalytic Asymmetric Iodoesterification of Simple Alkenes

et al. 2020

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Catalytic asymmetric iodoesterification of simple alkenes was achieved using a dinuclear zinc‐3,3′‐(R,S,S)‐bis(aminoimino)binaphthoxide (di‐Zn) complex. For iodoesterification using p‐methoxybenzoic acid, the N‐iodonaphthalenimide (NIN)‐I2 system was effective for producing iodoesters in a highly enantioselective manner. The synthetic utility of chiral iodo‐p‐methoxybenzoates was also demonstrated. The quartet of metal ionic bond, hydrogen bond, halogen bond, and π‐π stacking is harmonized on the single reaction sphere of di‐Zn catalyst for enabling the highly enantioselective catalytic asymmetric iodoesterification of simple alkenes for the first time.

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Highly Stereoselective Intermolecular Haloetherification and Haloesterification of Allyl Amides

Cited by 55 publications

References 76 publications

Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent

Nucleophile-Assisted Alkene Activation: Olefins Alone Are Often Incompetent

PIDA‐Mediated Formal Olefinic C=C Bond Cleavage of α‐Oxo‐Ketene N,N‐Acetals toward Substituted Oxazolines

Catalytic Asymmetric Iodoesterification of Simple Alkenes

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