Enantioselective [3 + 2] annulation of α-substituted allenoates with β,γ-unsaturated <i>N</i>-sulfonylimines catalyzed by a bifunctional dipeptide phosphine

Ni, Huanzhen; Yao, Weijun; Lü, Yixin

doi:10.3762/bjoc.12.37

Cited by 24 publications

(12 citation statements)

References 63 publications

(13 reference statements)

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“…On the basis of He’s work, Lu developed enantioselective [3 + 2] annulations of α , β -unsaturated imines with allenoates (Scheme 253). 323 In the presence of the chiral difunctional phosphine P63 (20 mol%), highly functionalized cyclopentenes, each bearing an all-carbon quaternary center, were obtained in moderate to good yields and with good to excellent enantioselectivities.…”

Section: Nucleophilic Phosphine Catalysis Of Allenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Nucleophilic Phosphine Catalysis Of Allenesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…Very recently, we reported an enantioselective [3+2] annulation reaction between ester‐activated α,β‐unsaturated N ‐sulfonylimines 38 and allenoates 37 , catalyzed by dipeptide phosphine P17 (Scheme ) . This transformation was based on the racemic version of the same reaction reported by Tian and He in 2013 …”

Section: Annulation Reactions Of Allenesmentioning

confidence: 80%

Enantioselective Construction of All‐Carbon Quaternary Stereogenic Centers by Using Phosphine Catalysis

Lü

2017

Asian J Org Chem

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104

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Abstract:The asymmetric construction of all-carbon quaternary stereogenic centers represents one of the most-challenging tasks in organic synthesis, and it has drawn continuous attentionf rom the synthetic community.A symmetric phosphine catalysis has progresseda ta na stonishingly rate over the past decade and it offers the efficient creation of ad iverser ange of structural architectures. In this Focus Review,s ynthetic methods based on phosphine catalysis for the enantioselectivec onstruction of all-carbon quaternary stereogenic centers are highlighted.

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“…20 Notably, sulfonylimine substrates have rarely been utilized in phosphine catalysis, and the winning catalyst P-7′ has a quite different dipeptide backbone, reinforcing the versatility of our catalyst system.…”

Section: [3 + 2] Annulations Of Allenesmentioning

confidence: 97%

“…Very recently, we developed an enantioselective [3 + 2] annulation of α-substituted allenoates with β,γ-unsaturated Nsulfonylimines for the synthesis of functionalized cyclopentenes bearing an all-carbon quaternary center (Scheme 12). 20 Notably, sulfonylimine substrates have rarely been utilized in phosphine catalysis, and the winning catalyst P-7′ has a quite different dipeptide backbone, reinforcing the versatility of our catalyst system.…”

Section: [3 + 2] Annulations Of Allenesmentioning

confidence: 99%

Amino Acid-Derived Bifunctional Phosphines for Enantioselective Transformations

et al. 2016

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Even though seminal reports on phosphine catalysis appeared in the 1960s, in the last few decades of the past century trivalent phosphines were viewed primarily as useful ligands for transition-metal-mediated processes. The 1990s saw revived interest in using phosphines in organic catalysis, but the key advances in asymmetric phosphine catalysis have all come within the past decade. The uniqueness of phosphine catalysis can be attributed to the high nucleophilicity of the phosphorus atom. In typical phosphine-catalyzed reactions, nucleophilic attacks of the phosphorus atom on electron-deficient multiple bonds create different reactive ylide-type intermediates. When such structurally diverse zwitterionic species react with a variety of suitable substrates, new reaction patterns are often discovered and a diverse array of reactions can be developed. In recent years, substantial progress has been made in the field of asymmetric phosphine catalysis; many new reactions have been discovered, and numerous enantioselective processes have been reported. However, we felt that powerful and versatile phosphine catalysts that can work for a wide range of asymmetric reactions are still lacking. We therefore set our goal to develop a family of easily derived phosphine catalysts that are efficient in asymmetric induction for a broad range of phosphine-mediated transformations. This Account describes our efforts in the past few years on the development of amino acid-based bifunctional phosphines and their applications to enantioselective processes. Building upon our previous success in primary-amine-mediated enamine catalysis, we first established that bifunctional phosphines could be readily prepared from amino acids. In most of our studies, we chose threonine as the key backbone for catalyst development, and threonine-based monoamino acid or dipeptide bifunctional phosphines have displayed remarkable stereochemical control. We began our investigations by demonstrating the usefulness of our phosphine catalysts in aza-Morita-Baylis-Hillman (aza-MBH) and MBH reactions. We then showed the great power of amino acid/dipeptide phosphines in a wide range of [3 + 2] annulation processes, including [3 + 2] cycloaddition of allenoates to acrylates/acrylamides, [3 + 2] annulation of imines with allenoates, and [3 + 2] cyclization employing MBH carbonates and activated alkenes. By utilizing α-substituted allenoates and activated alkenes, we developed an enantioselective [4 + 2] annulation to access functionalized cyclohexenes. We also devised a novel enantioselective [4 + 2] annulation process by using α-substituted allenones for the construction of 3,4-dihydropyrans. With the use of β'-acetate allenoate, a [4 + 1] annulation process has been designed to access chiral spiropyrazolones. Another array of reactions that make use of the basicity of zwitterionic phosphonium enolate intermediates have been successfully attained, including the first phosphine-catalyzed asymmetric Michael addition, enantioselective allylic substitution of MBH carbo...

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Enantioselective [3 + 2] annulation of α-substituted allenoates with β,γ-unsaturated N-sulfonylimines catalyzed by a bifunctional dipeptide phosphine

Cited by 24 publications

References 63 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Enantioselective Construction of All‐Carbon Quaternary Stereogenic Centers by Using Phosphine Catalysis

Amino Acid-Derived Bifunctional Phosphines for Enantioselective Transformations

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