N -Acyliminium ion chemistry and palladium catalysis: a useful combination to obtain bicyclic heterocycles

Karstens, Willem F. J.; Klomp, Dirk; Rutjes, Floris P. J. T.; Hiemstra, Henk

doi:10.1016/s0040-4020(01)00364-7

Cited by 46 publications

(16 citation statements)

References 44 publications

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“…The reaction of 4acetoxy-5-ethoxypyrrolidinone 186 with propargylsilane 184b under the same reaction conditions afforded the corresponding product 187 in 37% yield and with very high trans selectivity (trans/cis = 98:2) (Scheme 72, equation 2). 51 The N-acyliminium ion generated from 188 was trapped with allyltrimethylsilane in the presence of boron trifluoride-diethyl ether complex to give allylated product 189 in 71% yield (Scheme 73). 46 The zinc triflate catalysed reaction of allyltrimethylsilane with the 5-hydroxy- ( 1 )…”

Section: Scheme 71mentioning

confidence: 99%

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I)

Yazici¹,

Pyne²

2009

Synthesis

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I n t e r m o l e c u l a r A d d i t i o n R e a c t i o n s o f N -A c y l i m i n i u m I o n s ( P a r t I )Abstract: This review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic Nacyliminium ions. This is an update of an earlier review in 2000 on this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. This review is presented in two parts, with the first part dealing with acyclic and pyrrolidinone-based N-acyliminium ions. Part II continues with other five-membered heterocyclic derivatives and higher systems. IntroductionThis review highlights the advances in the literature up to July 2008 on the intermolecular reactions of acyclic and cyclic N-acyliminium ions. This is an update of an earlier review in 2000 2 on this topic and does not include intramolecular addition reactions to N-acyliminium ions which was recently reviewed. 3 A review article on addition reactions to related, but less reactive, N-acylimines has also been recently published. 4The highly reactive nature of N-acyliminium ions require that they are generated in situ usually in the presence of the other reactive, electron-rich, nucleophilic partner (NuY, Y = metal, SiR 3 , SnR 3-, etc.). In general these intermediates are generated from more stable and isolatable asubstituted N-acylamines of the type 1 by treatment with a Lewis acid or sometimes a protic acid (Scheme 1). The reaction of 2 with a nucleophilic species (NuY) then gives a-substituted N-acylamine 3. Compounds 1-3 can be acyclic systems or R 1 and R 2 , R 2 and R 3 , R 1 and R 3 can be taken together to form part of a ring system as shown in the general structures 4, 5, and 6.Compounds like 1 (X = OH and NHCO 2 R) are most likely formed in situ from the Lewis acid promoted threecomponent, one-pot coupling reactions of carbamates, aldehydes (or acetals) and silyl nucleophiles or electronrich aromatic nucleophiles (Scheme 2). 5,6N-Acyliminium ions like 11 can also be generated in dichloromethane solution, in the absence of nucleophiles, by the electrochemical oxidation of N-trimethylsilylmethyl carbamates like 10 (Scheme 3). These intermediates have been characterised spectroscopically and were subDownloaded by: Florida International University. Copyrighted material.

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Section: Scheme 71mentioning

confidence: 99%

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I)

Yazici¹,

Pyne²

2009

Synthesis

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“…Treatment of allene containing lactams or oxazolidinones with allyl halides in the presence of PdCl 2 (CH 3 CN) 2 as the catalyst (10 mol %) results in a cyclization/coupling reaction yielding bicyclic systems such as pyrrolizidinones and indolizidinones, in which the allyl moiety has been incorporated (eq 28). 46 Two mechanistic pathways have been postulated for this type of reaction. One is the intramolecular attack of the nitrogen nucleophile onto the activated allene-Pd II complex, followed by insertion of allyl bromide into the resulting σ-vinylpalladium complex and dechloropalladation, which regenerates PdCl 2 .…”

Section: Palladium(ii)-catalyzed/promoted Addition To Allenesmentioning

confidence: 99%

Dichloro Bis(acetonitrile) Palladium

Carretero

Arrayás

2008

Encyclopedia of Reagents for Organic Synthesis

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“…The palladium(0)-catalysed coupling reaction of unsaturated halides, triflates, hypervalent iodonium salts or allyl halides with allenes bearing an amino group separated from the carbon atom by one to four carbon atoms (155) has been studied by several groups. 38,[83][84][85][86][87][88][89][90] These reactions have permitted the synthesis of a large variety of three to six-membered azacycles (156, 157). As previously discussed in section 3.2, two plausible mechanisms may be envisaged (Scheme 63).…”

Section: Scheme 61mentioning

confidence: 99%

Cyclisations Involving Attack of Carbo- and Heteronucleophiles on Carbon-Carbon π-Bonds Activated by Organopalladium Complexes

Balme¹,

Bouyssi²,

Lomberget³

et al. 2003

Synthesis

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In the late 1980's, a new process based on an intramolecular palladium-mediated cyclisation coupled with a carbon-carbon bond forming reaction appeared in the literature. Since the first report, many novel ring systems have been synthesized using this methodology. The aim of this present review article is to summarise a number of synthetic applications of this new process developed over the last fifteen years.

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N -Acyliminium ion chemistry and palladium catalysis: a useful combination to obtain bicyclic heterocycles

Cited by 46 publications

References 44 publications

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I)

Intermolecular Addition Reactions of N-Acyliminium Ions (Part I)

Dichloro Bis(acetonitrile) Palladium

Cyclisations Involving Attack of Carbo- and Heteronucleophiles on Carbon-Carbon π-Bonds Activated by Organopalladium Complexes

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