A Simple and General Platform for Generating Stereochemically Complex Polyene Frameworks by Iterative Cross‐Coupling

Lee, Suk Joong; Anderson, Thomas M.; Burke, Martin D.

doi:10.1002/anie.201004911

Cited by 118 publications

(19 citation statements)

References 45 publications

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“…The capacity of olefinic stereochemical elements pre-installed in shelf-stable bifunctional MIDA boronate building blocks to be faithfully translated into growing targets by using mild and stereospecific cross-coupling methods simplifies this type of complex problem. 165–166, 179 Specifically in this case, a cis -bifunctional vinyl MIDA boronate building block was iteratively cross-coupled to unite the two key fragments of the polyene core of myxalamide A in a stereospecific fashion. Moreover, no protecting groups were required, as the cross-coupling reactions proceeded in the presence of two free alcohols.…”

Section: Iterative Cross-coupling With Mida Boronatesmentioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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Small molecules have extensive untapped potential to benefit society, but access to this potential is too often restricted by limitations inherent to the customized approach currently used to synthesize this class of chemical matter. In contrast, the “building block approach”, i.e., generalized iterative assembly of interchangeable parts, has now proven to be a highly efficient and flexible way to construct things ranging all the way from skyscrapers to macromolecules to artificial intelligence algorithms. The structural redundancy found in many small molecules suggests that they possess a similar capacity for generalized building block-based construction. It is also encouraging that many customized iterative synthesis methods have been developed that improve access to specific classes of small molecules. There has also been substantial recent progress toward the iterative assembly of many different types of small molecules, including complex natural products, pharmaceuticals, biological probes, and materials, using common building blocks and coupling chemistry. Collectively, these advances suggest that a generalized building block approach for small molecule synthesis may be within reach.

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Section: Iterative Cross-coupling With Mida Boronatesmentioning

confidence: 99%

Towards the generalized iterative synthesis of small molecules

2018

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“…As such, the identification of proper reaction conditions to enable orthogonal reactivities is necessary but represents a challenge. Guided by the above-mentioned concept, we reasoned the sp 3 -hybridized MIDA (N-methyliminodiacetyl) boron might be an optimal choice [29][30][31][32] . Early studies reveal the notable stability of MIDA boron towards diverse reaction conditions.…”

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confidence: 99%

Regio- and stereoselective synthesis of tetra- and triarylethenes by N-methylimidodiacetyl boron-directed palladium-catalysed three-component coupling

Lin

Schäfers

et al. 2019

Commun Chem

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The flexible synthesis of tetra-and triarylethenes bearing different aryl groups has been a long-standing challenge in organic synthesis. Here we report a palladium-catalysed syndiarylation of arylethynyl N-methyliminodiacetyl (MIDA) boronates. The products, triarylalkenyl N-methyliminodiacetyl boronates, allow a step-economic and modular synthesis of tetra-or triarylethenes via a subsequent stereospecific Suzuki-Miyaura coupling reaction or base-promoted protodeborylation, respectively. Use of the sp 3-B(MIDA) masked aryl alkyne is the key factor for success by offering an exceptionally good regioselectivity for the boronretentive coupling. The unusual regioselectivity is believed to arise from the stabilization due to the strong electron donation from the C−Pd σ bond to the p-orbital of boron in the transition state of migratory insertion. A broad range of differently substituted tetra-and triarylethenes are constructed in good yields and geometrical control. Synthetic manipulation of the C-B bond also enables the facile construction of several other types of tetra-substituted alkenes.

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“…Thus, reaction of 38 with an excess of the boronic acid generated upon treatment of 36 (2.25 equivalents) with an aqueous solution of NaOH, catalyzed by Pd(OAc) 2 /XPhos ( 30 ) in the presence of Cs 2 CO 3 , led to ( Z , Z , E , E , E )‐pentaenyl‐MIDA boronate 39 in 46 % yield. Finally, the pentaenylboronic acid derived from 39 (1.91 equivalents) underwent cross‐coupling with ( E , E )‐dienyliodide 40 using Pd(OAc) 2 /SPhos ( 37 ) as catalyst to afford unstable ( E , E , Z , Z , E , E , E )‐heptaene 41 as a model fragment of the polyketide‐derived polyenic macrolactone vacidin A 33 [42a] …”

Section: ω‐Bisfunctionalized Unsaturated Reagentsmentioning

confidence: 99%

“…As a representative member of the bis‐functionalized trienyl‐MIDA boronates, the synthesis of C 6 ω‐iodotrienyl‐MIDA boronate 51 a was carried out by the alkene chain extension protocol from precursor iododienyl‐MIDA boronate 34 using ( E )‐triethyl(2‐(tributylstannyl)vinyl)germane 140 (Scheme 15 A). Thus, the Stille–Kosugi–Migita cross‐coupling of 34 with Sn/Ge bismetallated olefin 140 using CuTC (Copper(I) thiophene‐2‐carboxylate, 141 ) and Pd(PPh 3 ) 4 in DMF (78 % yield), was followed by the stereospecific halodegermylation of the trienylgermanium precursor 142 with iodine, which promoted the exchange to 51 a in 85 % yield [42a] …”

Section: ω‐Bisfunctionalized Unsaturated Reagentsmentioning

confidence: 99%

Synthesis of Symmetrical and Nonsymmetrical Polyenes by Iterative and Bidirectional Palladium‐Catalyzed Cross‐Coupling Reactions

Rivas

Areal

Mora

et al. 2020

Chemistry A European J

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Bifunctional unsaturated reagents designed to undergo palladium‐catalyzed cross‐coupling reactions with complementary polyenyl connective fragments are highly useful for the undoubtedly challenging synthesis of polyenes. The current toolkit of building blocks for the bidirectional formation of Csp2−Csp2 single bonds of polyenes includes homo‐bisfunctionalized reagents with equal or unequal reactivity (due to steric and/or electronic factors), and hetero‐bisfunctionalized counterparts containing either two different nucleophiles, two electrophiles or one of these functionalities and a latent nucleophile that can be unmasked when desired. The combination of these bifunctional linchpin reagents using tactics that modulate the reactivity of each terminus in order to achieve the required connection have streamlined the synthesis of polyenes of great complexity using (iterative) cross‐coupling methods for Csp2−Csp2 bond formation. Reaction conditions for the Pd‐catalyzed cross‐coupling reactions are mild and functional‐group‐tolerant, and therefore these protocols allow to construct the polyene structures using shorter unsaturated reactants with the desired geometries, since in general the products preserve the stereochemical information of the connected cross‐coupling partners.

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A Simple and General Platform for Generating Stereochemically Complex Polyene Frameworks by Iterative Cross‐Coupling

Cited by 118 publications

References 45 publications

Towards the generalized iterative synthesis of small molecules

Towards the generalized iterative synthesis of small molecules

Regio- and stereoselective synthesis of tetra- and triarylethenes by N-methylimidodiacetyl boron-directed palladium-catalysed three-component coupling

Synthesis of Symmetrical and Nonsymmetrical Polyenes by Iterative and Bidirectional Palladium‐Catalyzed Cross‐Coupling Reactions

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