Synthesis of 2,6-disubstituted piperidine alkaloids from ladybird beetles Calvia 10-guttata and Calvia 14-guttata

Kubizna, Peter; S̆pánik, Ivan; Kožı́šek, Jozef; Szolcsányi, Peter

doi:10.1016/j.tet.2010.01.106

Cited by 42 publications

(17 citation statements)

References 37 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The cis-disubstituted piperidine 23 was obtained with high yield and diastereoselectivity, with partial transesterification occurring during the transformation. Further transformation of 23 in calvine via ethylene oxide opening with 23b, followed by ring-closing into the seven-membered lactone, has already been reported in the literature [63] (for a recent synthesis of calvine see [64] Scheme 6 Bi(OTf) 3 ·4H 2 O-catalyzed allylation using a functionalized allylsilane 80 T. Ollevier…”

Section: Bismuth Triflate-catalyzed Sakurai Allylation Reactionmentioning

confidence: 90%

Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines

Ollevier

2011

Bismuth-Mediated Organic Reactions

View full text Add to dashboard Cite

Bismuth triflate was found to be an efficient catalyst both in the Mannich-type reaction of silyl enolates and in the Sakurai reaction of allyltrimethylsilane with N-alkoxycarbonylamino sulfones. The reactions proceeded smoothly with a low catalyst loading of Bi(OTf)(3)·4H(2)O (0.5-5.0 mol%) to afford the corresponding protected β-amino carbonyl compounds and homoallylic amines in very good yields (up to 96%). The latter compounds could also be obtained via a bismuth-mediated three-component reaction. We have also developed an efficient vinylogous Mukaiyama aldol reaction of 2-(trimethylsilyloxy)furan with various aromatic aldehydes mediated by bismuth triflate in a low catalyst loading (1 mol%). The reaction proceeds rapidly and affords the corresponding 5-[hydroxy(aryl)methyl]furan-2(5H)-ones in high yields with good to very good diastereoselectivities (diastereoisomeric ratios>98:2). Such selectivities, although previously reported with other Lewis acids, could be achieved with a much lower catalyst loading. 5-[Hydroxy(alkyl)methyl]furan-2(5H)-ones derived from ketones could also be obtained with good diastereoselectivities. The vinylogous Mukaiyama aldol reaction has also been extended to 2,2-dimethyl-6-methylene-4-(trimethyl-silyloxy)-1,3-diox-4-ene using 1 mol% of Bi(OTf)(3)·4H(2)O.

show abstract

Section: Bismuth Triflate-catalyzed Sakurai Allylation Reactionmentioning

confidence: 90%

Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines

Ollevier

2011

Bismuth-Mediated Organic Reactions

View full text Add to dashboard Cite

show abstract

“…15 A cyclizative carboamination of the alkenylamines 11 carried out under these conditions and involving a carbonylation reaction, was used as the key step for the synthesis of the optically pure piperidine alkaloids 12-14 isolated from ladybird beetles (Scheme 7). 16 Noteworthy is the possibility to influence the stereoselectivity of the cyclization by adding a different…”

Section: Scheme 5 Conversion Of N-46-dienyl-β-ketoamides Into Pyrrolmentioning

confidence: 99%

Intramolecular Oxidative Palladium-Catalyzed Amination Involving Double C–H Functionalization of Unactivated Olefins

et al. 2017

View full text Add to dashboard Cite

Intramolecular palladium-catalyzed amination reactions are becoming important tools for the synthesis of various nitrogen-containing heterocycles. This account highlights the developments achieved in this field by domino processes in oxidative conditions using unactivated olefins, due to their advantages in terms of step economy and efficiency. These reactions involve the change of oxidation state in the palladium intermediate, requiring the presence of an oxidizing agent to regenerate the catalytic cycle. This kind of additive is essential for the success of the reaction and it can also furnish nucleophilic species that are incorporated into the final product. Reactions can occur at either the intra/intra- or intra/intermolecular level, providing valuable methodologies for the preparation of (poly)heterocyclic scaffolds. Besides, procedures based on the use of strengthened catalytic systems, more recently, disclosed intriguing conditions have enlarged the possibility to modulate the substrate reactivity. Perspectives in this field are directed to the discovery of new reaction conditions, focusing on the employment of oxidatively stable ligands useful for the asymmetric catalysis.1 Introduction2 Carboamination Reactions2.1 Pd(0)/Pd(II)2.2 Pd(II)/Pd(IV)3 Aminooxygenation Reactions3.1 Pd(0)/Pd(II)3.2 Pd(II)/Pd(IV)4 Diamination Reactions4.1 Pd(0)/Pd(II)4.2 Pd(II)/Pd(IV)5 Aminohalogenation Reactions5.1 Pd(0)/Pd(II)5.2 Pd(II)/Pd(IV)6 Conclusions

show abstract

“…The aminocyclization-methoxycarbonylation sequence of alkenylamine 135 performed by catalytic PdCl 2 and CuCl 2 in MeOH under the CO/O 2 atmosphere provided an inseparable mixture of the piperidines 136 in the 68% yield (Scheme 58). 70 The final catalytic debenzylation of methylesters gave an easily separable mixture of the target piperidines 137 and 138 in 81% combined yield and in a 1 : 3 ratio in favour of the 2,6trans-configured compound 136, which is the most challenging between the two diastereoisomeric 2,6-disubstituted piperidine alkaloids isolated from ladybird beetles of the genus Calvia.…”

Section: Cyclization-methoxycarbonylationsmentioning

confidence: 99%

Recent advances in heterobimetallic palladium(ii)/copper(ii) catalyzed domino difunctionalization of carbon–carbon multiple bonds

et al. 2014

View full text Add to dashboard Cite

show abstract

Synthesis of 2,6-disubstituted piperidine alkaloids from ladybird beetles Calvia 10-guttata and Calvia 14-guttata

Cited by 42 publications

References 37 publications

Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines

Bismuth-Catalyzed Addition of Silyl Nucleophiles to Carbonyl Compounds and Imines

Intramolecular Oxidative Palladium-Catalyzed Amination Involving Double C–H Functionalization of Unactivated Olefins

Recent advances in heterobimetallic palladium(ii)/copper(ii) catalyzed domino difunctionalization of carbon–carbon multiple bonds

Contact Info

Product

Resources

About