Organocatalytic Approach to Benzofused Nitrogen‐Containing Heterocycles: Enantioselective Total Synthesis of (+)‐Angustureine

Fustero, Santos; Moscardó, Javier Ruiz; Jiménez, Daniel; Pérez‐Carrión, María Dolores; Sánchez‐Roselló, María; Pozo, Carlos del

doi:10.1002/chem.200801480

Cited by 117 publications

(37 citation statements)

References 84 publications

(18 reference statements)

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“…[25] The absolute configuration of the products was established by the synthesis of the alkaloid (+)-angustureine. Similar to the first publication 20 mol % of the bis-trifluoromethylated arylprolinol TMS ether 13 as catalyst and benzoic acid as an additive was used.…”

Section: Intramolecular Aza-michael Reactionsmentioning

confidence: 99%

Organocatalytic Asymmetric Aza‐Michael Additions

Enders

Wang

Liebich

2009

Chemistry A European J

449

147

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The catalytic aza-Michael addition is an important reaction within synthetic organic chemistry, given the significance of the biologically and synthetically interesting products, such as beta-amino acids and beta-lactams. In the last decade organocatalysis emerged as a powerful tool in asymmetric synthesis and had a large impact on the development of asymmetric and catalytic conjugate additions of nitrogen nucleophiles to Michael acceptors. In this review a first summary of the recent rapid progress of asymmetric organocatalyzed aza-Michael reactions is presented.

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Section: Intramolecular Aza-michael Reactionsmentioning

confidence: 99%

Organocatalytic Asymmetric Aza‐Michael Additions

Enders

Wang

Liebich

2009

Chemistry A European J

449

147

View full text Add to dashboard Cite

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“…After 12 h, THF was removed in vacuo, brine (100 mL) was added and extracted with ether (3 × 100 mL). The dried (MgSO 4 ) extract was concentrated in vacuo , purified by chromatography over silica gel, eluting with 1–20% EtOAc/hexanes to give 33 21a (2.43 g, 12.23 mmol, 96% over 3 steps) as a colorless oil. IR (neat) 3364, 3075, 2975, 2931, 1700, 1642, 1365, 1172 cm −1; 1 H NMR (400 MHz, CDCl3) δ 5.80 (ddt, J = 13.3, 10.1, 6.6 Hz, 1H), 5.02 (dq, J = 17.2, 1.7 Hz, 2H), 4.52 (br s, 1 H), 3.12–3.15 (m, 2H), 2.07–2.12 (m, 2H), 1.48–1.55 (m, 3H), 1.47 (s, 9H), 1.43–1.45 (m, 1H); 13 C NMR (100 MHz, CDCl3) δ 156.0, 138.5, 114.6, 79.0, 40.4, 33.3, 29.5, 28.4, 26.0; HRMS (EI+) calcd.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Approach to Quinolizidines: Total Synthesis of Cermizine D and Formal Syntheses of Senepodine G and Cermizine C

et al. 2013

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The formal total syntheses of C5-epi-senepodine G and C5-epi-cermizine C have been accomplished through a novel diastereoselecetive, intramolecular amide Michael addition process. The total synthesis of cermizine D has been achieved through use of an organocatalyzed, heteroatom Michael addition to access a common intermediate. Additional key steps of this sequence include a matched, diastereoselective alkylation with an iodomethylphenyl sulfide and sulfone-aldehyde coupling/reductive desulfurization sequence to combine the major subunits. The utility of a Hartwig-style C-N coupling has been explored on functionally dense coupling partners. Diastereoselective conjugate additions to α,β-unsaturated sulfones has been investigated which provided the key sulfone intermediate in just six steps from commercially available starting materials. The formal syntheses of senepodine G and cermizine C have been accomplished through an intramolecular cyclization process of a N-Boc protected piperidine sulfone.

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“…An intramolecular aza-Michael reaction was reported by Fustero and co-workers in 2008, [55] their optimized approach was carried out at À30 8C with silyl ethers of diarylprolinol (13a or 13c) in CHCl 3 (Scheme 27), which gave the product 87 with good yields (up to 72%) and excellent enantioselectivities (up to 99% ee).…”

Section: Hetero-michael Reactionmentioning

confidence: 98%

Asymmetric Synthesis with Silicon‐Based Bulky Amino Organocatalysts

Shi

2010

Adv Synth Catal

218

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Recent years have witnessed an explosive growth in the field of amino organocatalysis, especially in asymmetric enamine and iminium catalysis. Except for the obvious interaction between organocatalyst and substrate, the impact of bulky side group ons stereoselectivity is not as simple as one could imagine. Within the development of bulky sitestereoselective organocatalysts, functional silyl organocatalysts with a bulky silicon group are promising and meet the high standards of modern synthetic methods. This review focuses on the recent advances in the synthetic applications of silicon-based, bulky amino organocatalysts in which catalysts containing an organosilicon moiety or group play a formative role in controlling both the course of the reaction as well as the stereoselectivity.

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Organocatalytic Approach to Benzofused Nitrogen‐Containing Heterocycles: Enantioselective Total Synthesis of (+)‐Angustureine

Cited by 117 publications

References 84 publications

Organocatalytic Asymmetric Aza‐Michael Additions

Organocatalytic Asymmetric Aza‐Michael Additions

Enantioselective Approach to Quinolizidines: Total Synthesis of Cermizine D and Formal Syntheses of Senepodine G and Cermizine C

Asymmetric Synthesis with Silicon‐Based Bulky Amino Organocatalysts

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