Cleavage of a chiral auxiliary using RCM on an especially sterically crowded alkene: Syntheses of chiral carbo- and heterocycles

Spino, Claude; Boisvert, Luc; Douville, Jasmin; Roy, Stéphanie; Lauzon, Sophie; Minville, Joannie; Gagnon, David; Beaumier, Francis; Chabot, Christine

doi:10.1016/j.jorganchem.2006.07.028

Cited by 15 publications

(6 citation statements)

References 66 publications

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“…We figured that three products could potentially be formed during the RCM of enone 33 : the desired 8-membered ring 45 (Scheme ), as well as the 5-membered ring 46 or the 6-membered ring 47 (Figure ). Initiation at the enone alkene is unlikely, and according to previous work in our laboratory, 6-membered rings are not formed when an all-carbon quaternary center is present at this position . Hence, the eight-membered ring 45 should be the major product even though it is not entropically favored .…”

Section: Resultsmentioning

confidence: 72%

Stereoselective Synthesis of (+)-Euphococcinine and (−)-Adaline

et al. 2009

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We describe the syntheses of (+)-euphococcinine and (-)-adaline, two naturally occurring alkaloids containing a quaternary carbon bearing a nitrogen atom. Key features of the syntheses are a 3,3-sigmatropic rearrangement to give an all-carbon quaternary center, a ring-closing alkene metathesis to give an 8-membered ring, and the use of a single enantiomer of p-menthane-3-carboxaldehyde to make two natural alkaloids of opposite configuration.

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Section: Resultsmentioning

confidence: 72%

Stereoselective Synthesis of (+)-Euphococcinine and (−)-Adaline

et al. 2009

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“…Так, заміна каталізатора Граббса ІІ на каталіза- тор Нолана при циклізації аліламіду 39 приво-дить до утворення азепану 41 [24] (схема 16).…”

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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“…When R 1 or R 2 in 83 is a hydrogen, X can be anyone of carbon, oxygen, nitrogen, or sulfur and excellent yields of five and six-membered rings (84, n = 0 or 1) carbo-or heterocycles can be obtained. 56 Scheme 22 shows typical examples and a few interesting notes are in order at this point. 50,56 Five-membered rings (86) form much faster and in higher yields than the homologous six-membered rings (87).…”

Section: Introducing a Heteroatommentioning

confidence: 99%

“…56 Scheme 22 shows typical examples and a few interesting notes are in order at this point. 50,56 Five-membered rings (86) form much faster and in higher yields than the homologous six-membered rings (87). In fact, all-carbon quaternary chiral centers (83, X, R 1 , R 2 = C, Scheme 22) prevent the formation of six-membered rings all-together (88) while five-membered rings are formed, albeit using a high catalyst loading (89).…”

Section: Introducing a Heteroatommentioning

confidence: 99%