Advances in the Baylis–Hillman reaction-assisted synthesis of cyclic frameworks

Singh, Vijay; Batra, Sanjay

doi:10.1016/j.tet.2008.02.087

Cited by 510 publications

(94 citation statements)

References 288 publications

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“…The ultimate benefit is the synthetic feasibility of the products, the Morita-Baylis-Hillman adducts. 8 The predominating preparative utility of the MBH adducts originates from the susceptibility of the allylic / α,β-unsaturated system to nucleophilic substitution and addition. [3][4][5][6][7][8] The mechanism and the position of the displacements strongly depend on the structure of the substrates and the manipulation conditions (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

“…8 The predominating preparative utility of the MBH adducts originates from the susceptibility of the allylic / α,β-unsaturated system to nucleophilic substitution and addition. [3][4][5][6][7][8] The mechanism and the position of the displacements strongly depend on the structure of the substrates and the manipulation conditions (Scheme 2). Attack on the primary MBH adducts, allyl alcohols, typically proceeds according to a mechanism of Michaeltype addition of a nucleophile to the electrophilic terminal carbon of an activated unsaturated system (Scheme 2A).…”

Section: Introductionmentioning

confidence: 99%

“…[3][4][5][6][7][8] The potential of the reactivity of MBH adducts towards phosphorus nucleophiles seems not to have been extensively explored as yet and hardly extends beyond a few types of simple P-compounds and MBH adducts. Dialkyl and trialkyl phosphites, which substitute for the electrophilic components according to the Arbuzov reaction mechanism following the general rules outlined in Scheme 2, have been the most documented.…”

Section: Introductionmentioning

confidence: 99%

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P-C bond formation in reactions of Morita-Baylis-Hillman adducts with phosphorus nucleophiles

Talma¹,

Mucha²

2016

Arkivoc

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Morita-Baylis-Hillman adducts (e.g., activated allyl acetates or bromides) are an unprecedented trifunctional synthetic platform for diverse types of nucleophilic displacements, additions and rearrangements. These reactions can proceed in an inter-or intramolecular manner, and with stereoselective induction. Accordingly, they contribute, as the key steps, to numerous synthetic pathways, including the total syntheses of natural products of various classes and to novel strategies leading to medicinally relevant compounds and commercialized drugs. The synthetic feasibility of the Morita-Baylis-Hillman adducts in organophosphorus chemistry has been explored to a relatively low extent. In this review, we summarize the current state of the art on the formation of the C-P bond by means of the title reactions. The scope of the processes, the stereochemistry of the products and their further synthetic relevance to obtain multifunctional compounds, including those that are biologically active, are summarized.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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P-C bond formation in reactions of Morita-Baylis-Hillman adducts with phosphorus nucleophiles

Talma¹,

Mucha²

2016

Arkivoc

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“…(5) It produces molecules containing a minimum of three proximal functional groups which are of tremendous potential in synthetic and mechanistic organic chemistry. In fact the wide popularity and applicability of this reaction can be easily understood by publications of a number of major [14][15][16][17][18][19][20][21][22] and mini reviews [23][24][25][26][27][28][29][30] and more than 3200 research articles during the past three decades.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Baylis-Hillman reaction: synthesis of heterocyclic molecules

Basavaiah¹,

Reddy²

2015

Arkivoc

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The Baylis-Hillman (BH) [also known as the Morita-Baylis-Hillman (MBH)] reaction is a versatile atom-economic C-C bond forming reaction between the α-position of activated alkenes and electrophiles under the influence of a catalyst and provides interesting classes of densely functionalized molecules. Its intramolecular version is yet another fascinating reaction by itself, producing various carbocylic and heterocyclic compounds of synthetic and medicinal relevance. Applications of the intramolecular Baylis-Hillman reaction in obtaining heterocyclic molecules of different ring sizes and also to the synthesis of various natural products/bioactive compounds containing heterocyclic frameworks are presented in this brief review.

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“…17 To the best of our knowledge there is no report about mechanistic study at present. In the synthesis of β-nitro-γ-enamines, 18 how are the two substrates activated by catalyst? In screening of catalysts, why is the best enantioselectivity obtained with the structure incorporating aromatic ring, thiourea and tertiary amine units?…”

mentioning

confidence: 99%

Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

Lu¹,

Wang²,

Wang³

2013

Bulletin of the Korean Chemical Society

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The enantioselective aza-Morita Baylis Hillman reaction of nitroalkene and N-tosylimine catalyzed by thiourea-tertiary amine has been investigated using density functional theory. Enantioselectivity is dominated by the cooperative effect of non-covalent and weak covalent interactions imposed by different units of catalyst. As Lewis base, the tertiary amine unit activates nitroalkene via weak covalent bond. The weak covalent interaction orients the reaction in a major path with smaller variations of this bond. The aromatic ring unit activates N-tosylimine via π-π stacking. The non-covalent interaction selects the major path with smaller changes of the efficient packing areas. Thiourea unit donates more compact H-bonded network for species of the major path. The calculated ee value in xylene solution phase (97.6%) is much higher than that in N,NDimethylformamide (27.2%). Our conclusion is also supported by NBO analysis.

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Advances in the Baylis–Hillman reaction-assisted synthesis of cyclic frameworks

Cited by 510 publications

References 288 publications

P-C bond formation in reactions of Morita-Baylis-Hillman adducts with phosphorus nucleophiles

P-C bond formation in reactions of Morita-Baylis-Hillman adducts with phosphorus nucleophiles

Intramolecular Baylis-Hillman reaction: synthesis of heterocyclic molecules

Theoretical Mechanism Studies on the Enantioselectivity of aza-MBH-type Reaction of Nitroalkene to N-tosylimine Catalyzed by Thiourea-tertiary Amine

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