Enantioselective Iridium-Catalyzed Allylic Substitutions with Hydroxamic Acid Derivatives as N-Nucleophiles

Gärtner, Martin; Jäkel, Mascha; Achatz, Manuel; Sonnenschein, Christoph; Tverskoy, Olena; Helmchen, Günter

doi:10.1021/ol200688d

Cited by 41 publications

(20 citation statements)

References 37 publications

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“…Starting material for the synthesis of (+)‐prosophylline was N‐ methoxylactam 55 (Scheme ), which was obtained from 2 d (93 % ee ) in 48 % yield in four steps using a route reported by us 1a. Standard protection gave O‐benzyl derivative 56 , which was suitable for addition of Grignard reagent 57 .…”

Section: Resultsmentioning

confidence: 99%

Addition of Organometallic Reagents to Chiral N‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines

Jäkel

Schnitzer

et al. 2013

Chemistry A European J

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Enantioselective iridium-catalyzed allylic substitutions were used to prepare N-allyl hydroxamic acid derivatives that were suitable for ring-closing metathesis, giving N-methoxylactams. Reactions of these derivatives with Grignard or organolithium compounds gave hemiaminals, which could be reduced diastereoselectively via acyliminium intermediates to give cis-piperidines or cis-pyrrolidines with substituents in the 2,6- or 2,5-positions, respectively. In addition, compounds with a quaternary carbon center could be synthesized by corresponding reactions with potassium cyanide/AcOH. The procedures were applied in the syntheses of alkaloids (-)-209D and (+)-prosophylline.

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Section: Resultsmentioning

confidence: 99%

Addition of Organometallic Reagents to Chiral N‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines

Jäkel

Schnitzer

et al. 2013

Chemistry A European J

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“…Схема 10 зовані аналоги природних алкалоїдів: лентигіно-зин [19], пуміліотоксин С [20], коніїн [21], (+)-α-конгідрин [22], а також полігідроксильовані пі-перидини [23] як потенційні інгібітори ензимів вуглеводного обміну. В такого типу перетворен-нях окрім комплексів Ru можуть бути використа-ні каталізатори на основі Pd [22] та Ir [23].…”

Section: схемаunclassified

“…В такого типу перетворен-нях окрім комплексів Ru можуть бути використа-ні каталізатори на основі Pd [22] та Ir [23]. У біль-шості випадків для таких процесів необхідна при-сутність кислоти Льюїса (PhBCl 2 ).…”

Section: схемаunclassified

Heterocyclization of amides of alkenylcarboxylic acids

Tsyzoryk¹,

Васькевич²,

Вовк³

2015

J. org. pharm. chem.

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(Ховейда, Граббса, Нолана), реакції мета-тезису, а також радикальних процесів у регіо-та стереоселективних циклізаціях амідів у м'яких умовах. Розглянуті синтетичні варіанти носять загальний характер і дозволяють поряд із процесами циклізації здійснювати спрямовану функціоналізацію O-, N-, S-вмісних малих та середніх гетероциклічних систем. HETEROCYCLIZATION OF AMIDES OF ALKENYLCARBOXYLIC ACIDS N.M.Tsyzoryk, A.I.Vaskevich, M.V.Vovk Key words: amides of alkenylcarboxylic acids; electrophilic intramolecular cyclization; lactones; lactams The latest published data on heterocyclization of amides of alkenylcarboxylic acids have been systematized. It has been proven that the electrophilic intramolecular cyclization reaction of functionally substituted olefins opened in the 70s of the last century is a convenient way of constructing different oxygen-, nitrogen-and sulfurcontaining heterocyclic compounds. It has been noted that anilides of unsaturated carboxylic acids as bifunctional nucleophilic systems containing alkenyl and aminocarbonyl functions are useful models to study the electrophilic cyclization reaction, which leads to formation of O-and N-containing heterocycles (lactones and lactams). The last of them belong to the important types of compounds used as key blocks in the synthesis of biologically active alkaloids and their analogues, pharmaceutical and agrochemical products. The effective approaches to the synthesis of new types of functionalized lactones and lactams have been developed; amides of 3-butenoic, 4-pentenoic and 5-hexenoic acids are often used as substrates for their design. Along with classical methods of synthesis of lactones and lactams the literary sources relating to the use of original catalytic electrophilic systems (Nolan, Grubbs, Hoveyda), the metathesis reaction and radical processes in regio-and stereoselective cyclization of amides under mild conditions have been analyzed and summarized in the article. The synthetic versions considered are general in nature and allow to perform the targeted functionalization of O-, N-, S-containing heterocyclic small and medium-sized systems along with the cyclization processes. ГЕТЕРОЦИКЛИЗАЦИИ АМИДОВ АЛКЕНИЛКАРБОНОВЫХ КИСЛОТ

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“…The enantioselectivity can be introduced as described above. 16 The direct allylation of alkyl halides results in a C(sp 3 )-C(sp 3 ) coupling. This catalysed reaction proceeds via an allyl alkyl cobalt intermediate.…”

Section: (C) Asymmetric Alkylation Of Nucleophiles; C-c Bond Formationmentioning

confidence: 99%

Allyl Alkyl Carbonates

Riemer¹

2014

Synlett

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Enantioselective Iridium-Catalyzed Allylic Substitutions with Hydroxamic Acid Derivatives as N-Nucleophiles

Cited by 41 publications

References 37 publications

Addition of Organometallic Reagents to Chiral N‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines

Addition of Organometallic Reagents to Chiral N‐Methoxylactams: Enantioselective Syntheses of Pyrrolidines and Piperidines

Heterocyclization of amides of alkenylcarboxylic acids

Allyl Alkyl Carbonates

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