Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids

Lauzon, Sophie; Tremblay, Francois; Gagnon, David; Godbout, Cédrickx; Chabot, Christine; Mercier-Shanks, Catherine; Perreault, Stéphane; DeSeve, Helene; Spino, Claude

doi:10.1021/jo800817p

Cited by 82 publications

(36 citation statements)

References 60 publications

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“…The five entries around −60° were indicative of a minor conformer in which the amide carbonyl group and the methoxy group were anti [i.e., CCDC 703912 [32], −67.7 (6)°; CCDC 1142231 [60], −57(3)° as Racid-enantiomer; CCDC 113953 [57], −58.4(9)°; CCDC 1310848 [58], −60(2)° and −51(2)°] (see Sections 2.7 and 2.8). The amine moiety of CCDC 703912 has a linear conjugated diene structure.…”

Section: Dihedral Angles Of Amide Carbonyl Group and Trifluoromethyl mentioning

confidence: 99%

“…The MTPA amide of CCDC 703912 [32], which has a linear conjugated diene moiety in the amine's substituent L 2 , exhibited another irregular dihedral angle of −162.7(5)°. One of the conformers of CCDC 1142231 [60] also exhibited the irregular dihedral angle (i.e., −148(2)° as Racid-enantiomer); these represent the minor conformer in which the amide carbonyl group and the methoxy group were anti.…”

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confidence: 99%

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Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database

2015

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Abstract:Conformations of the crystalline 3,3,3-trifluoro-2-methoxy-2-phenylpropanamide derivatives (MTPA amides) deposited in the Cambridge Structural Database (CSD) were examined statistically as Racid-enantiomers. The majority of dihedral angles (48/58, ca. 83%) of the amide carbonyl groups and the trifluoromethyl groups ranged from -30° to 0° with an average angle θ 1 of −13°. The other conformational properties were also clarified: (1) one of the fluorine atoms was antiperiplanar (ap) to the amide carbonyl group, forming a staggered conformation; (2) the MTPA amides prepared from primary amines showed a Z form in amide moieties; (3) in the case of the MTPA amide prepared from a primary amine possessing secondary alkyl groups (i.e., Mosher-type MTPA amide), the dihedral angles between the methine groups and the carbonyl groups were syn and indicative of a moderate conformational flexibility; (4) the phenyl plane was inclined from the O-Cchiral bond of the methoxy moiety with an average dihedral angle θ 2 of +21°; (5) the methyl group of the methoxy moiety was ap to the ipso-carbon atom of the phenyl group.

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Section: Dihedral Angles Of Amide Carbonyl Group and Trifluoromethyl mentioning

confidence: 99%

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confidence: 99%

Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database

2015

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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

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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“…[115] Here the auxiliary, p-menthane-3-carbaldehyde (223), readily prepared from menthone in either enantiomeric form, was used to induce stereochemistry and to also bias the equilibrium mixture of the required allylic azide. Thus, aldehyde 223 was treated with a vinyllithium reagent to give alcohol 224 which was then subjected to Mitsunobu reaction conditions to yield azide 225 in 98 % yield and in an excellent diastereomeric ratio (Ͼ 95:5).…”

Section: [33]-sigmatropic Rearrangementmentioning

confidence: 99%

“…[23,24,82,115,116] The direct diastereoselective addition of dialkyl phosphonates, to yield pyrrolidinylphosphonates, has also been illustrated. [102] Of the pyrrolidines synthesised from cyclic nitrone precursors, perhaps the most common target has been the radicamines A and B.…”

Section: Addition To Nitronesmentioning

confidence: 99%

Recent Developments in the Synthesis of Pyrrolidine‐Containing Iminosugars

et al. 2010

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As noted inhibitors of glycosidases, iminosugars have enormous therapeutic potential in the treatment of a number of diseases such as cancer, diabetes, and lysosomal storage disorders. Accordingly, much effort has been expended over the past decades in developing novel and efficient methodologies for the synthesis of iminosugars. This microreview highlights recent (post 2005) developments in the synthesis of pyrrolidine‐containing iminosugars and includes discussions of methodologies such as ring‐closing metathesis, aldol and pericyclic reactions, and protecting‐group free strategies.

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Sterically Biased 3,3-Sigmatropic Rearrangement of Chiral Allylic Azides: Application to the Total Syntheses of Alkaloids

Cited by 82 publications

References 60 publications

Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database

Characteristic Conformation of Mosher’s Amide Elucidated Using the Cambridge Structural Database

Heterocyclization of amides of alkenylcarboxylic acids

Recent Developments in the Synthesis of Pyrrolidine‐Containing Iminosugars

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