Chiral phosphine-catalyzed tunable cycloaddition reactions of allenoates with benzofuranone-derived olefins for a highly regio-, diastereo- and enantioselective synthesis of spiro-benzofuranones

De, Wang; Wang, Guo‐Peng; Sun, Yaoliang; Zhu, Shou‐Fei; Wei, Yin; Zhou, Qi‐Lin; Shi, Min

doi:10.1039/c5sc03135d

Cited by 88 publications

(22 citation statements)

References 111 publications

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“…In 2015, Wei, Shi, Zhou, and co-workers studied the chiral phosphine-catalyzed [3 + 2] annulations of allenoates with benzofuranone-derived olefins and observed substrate-dependent regioselectivities. 305 The enantioselective [3 + 2] cycloadditions in the γ - or α -addition modes were dependent on the substitution pattern of the allenic substrate. In the presence of ( R )- P32 (10 mol %) and 4 Å MS, the allenoates underwent γ -addition [3 + 2] cycloadditions with various benzofuranone-derived olefins in toluene/dichloromethane (1:1) at room temperature to produce a series of spirobenzofuranones in moderate to excellent yields and with high regioselectivities and enantioselectivities (Scheme 234).…”

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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“…Recently, Shi and co‐workers reported the phosphine‐catalyzed ( 67 ) asymmetric [3+2] cycloadditions of arylidene azlactones ( 65 ) with substituted allenoates ( 66 ), efficiently leading to spiro‐cycloadducts ( 68 ) in good to excellent yields (ranging from 71 and 95 %) and with perfect regio‐ and enantioselectivity (Scheme A) . A modest substrate scope (six compounds) was attained, in which, electron‐withdrawing ( 69 ) and meta ‐disubstituted phenyl groups ( 70 ) were well tolerated.…”

Section: Cycloadditionsmentioning

confidence: 99%

Recent Advances in Azlactone Transformations

2019

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Azlactones, also known as oxazolones, are versatile building blocks in organic synthesis due to the presence of multiple pro‐nucleophilic and electrophilic reactive sites. Recently, several elegant organo‐ and metal‐catalyzed studies have been described, allowing the stereocontrolled access to complex structures in only one or a few chemical steps. Moreover, the development of one‐pot, tandem and domino reactions greatly enhanced the azlactone scaffold potential. In this context, this review aims to cover novel methodologies, including a brief overview of oxazolones and Erlenmeyer azlactones preparation. New approaches towards classical reactions, such as dynamic kinetic resolution, cycloadditions, and conjugate additions will be presented as well as new methodologies involving photochemical and flow chemistry technology. Finally, for most studies, selected examples will be presented and mechanistic pathways and/or activating modes will be carefully discussed.

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“…Since Lu and coworkers reported the pioneering work of phosphine‐catalyzed [3 + 2] annulation reaction of 2,3‐butadienoates with imines (or alkenes) in 1995 (Equation a depicted in Scheme A), this kind of Lewis base‐catalyzed annulation reactions have been greatly developed. As an important substrate, allenoates can be activated by nucleophilic phosphine and exhibit diverse reactivity, for example, they can function as two‐, three‐, or four‐carbon synthons when they react with different reagents (Equations b–g depicted in Scheme A). In addition, the alkenyl and alkynyl ketones have also been explored to participate in phosphine‐catalyzed [3 + 2] and [3 + 3] annulation reactions (Equation h depicted in Scheme B).…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation toward organophosphine‐catalyzed [3 + 3] annulation of Morita–Baylis–Hillman carbonates with azomethine imines: Mechanism, origin of stereoselectivity, and role of catalyst

Zhang

Qiao

Wang

et al. 2017

Int J of Quantum Chemistry

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A computational study on the detailed mechanism and stereoselectivity of the chiral phosphinecatalyzed C(sp 2 )AH activation/[3 1 3] annulation between Morita-Baylis-Hillman (MBH) carbonates and C,N-cyclic azomethine imines has been performed. Generally, the catalytic cycle consists of two stages, that is, C(sp 2 )AH activation companied by the dissociation of the t-BuOCO 2 2 group forming phosphonium enolate, and [3 1 3] cycloaddition process followed by regeneration of the catalyst. The calculated results indicate that C(sp 2 )AH activation is ratedetermining while [3 1 3] cycloaddition is stereoselectivity-determining. Furthermore, the advantageous hydrogen bond interactions and less steric hindrance in the RR configurational CAC bond forming transition states should be responsible for the favorability of RR-configured product among the four possible products. The special role of the organocatalyst was also identified by natural bond orbital (NBO) and global reactivity index (GRI) analyses. The mechanistic insights obtained in the present study should be useful for understanding the novel organocatalytic C (sp 2 )AH activation and cycloaddition cascade reaction of MBH carbonates, and thus provide valuable clues on rational design of efficient organocatalysts for the C(sp 2 )AH activation/ functionalizations. K E Y W O R D S [3 1 3] cycloaddition, DFT, organophosphine catalysis, stereoselectivity Int J Quantum Chem. 2017;117:e25367.

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Chiral phosphine-catalyzed tunable cycloaddition reactions of allenoates with benzofuranone-derived olefins for a highly regio-, diastereo- and enantioselective synthesis of spiro-benzofuranones

Abstract: The first regioselective catalytic asymmetric [3 + 2] cycloaddition of benzofuranone-derived olefins with allenoates and substituted allenoates has been developed in the presence of (R)-SITCP.

Cited by 88 publications

References 111 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Recent Advances in Azlactone Transformations

Theoretical investigation toward organophosphine‐catalyzed [3 + 3] annulation of Morita–Baylis–Hillman carbonates with azomethine imines: Mechanism, origin of stereoselectivity, and role of catalyst

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