Directed asymmetric synthesis with boronic esters

Matteson, Donald S.; Sadhu, Kizhakethil Mathew; Ray, Rahul; Jesthi, Pradipta K.; Peterson, Mark L.; Majumdar, D.; Tsai, David J. S.; Hurst, Gerald D.; Erdık, Ender

doi:10.1016/0022-328x(85)87086-8

Cited by 10 publications

(2 citation statements)

References 33 publications

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“…1c). [4][5][6][7] As an example, in this iterative two-step process, alkyl-substituted boronic ester 1 was treated with dihalomethyl lithium (e.g. LiCHCl2, 2) and ZnCl2 to generate α-halo boronic ester 3.…”

Section: Substrate-controlled Homologation Of Boronic Estersmentioning

confidence: 99%

Lithiation–borylation methodology in the total synthesis of natural products

2022

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Robust synthetic methods which show broad substrate scope are of great utility in the synthesis of complex organic molecules. Within this arena, synthetic methods employing boronic esters are especially useful since they undergo a wide variety of transformations with very high levels of stereoselectivity. In particular, boronic esters can undergo single or multiple homologations using enantioenriched metal carbenoids. The addition of a suitable enantioenriched lithium or magnesium carbenoid to a boronic ester, with subsequent 1,2-migration, gives a homologated boronic ester with high stereocontrol. The process, termed lithiation-borylation, can be iterated allowing a carbon chain to be "grown" one atom at time with remarkable precision. The iterative homologation has been likened to a molecular assembly line and resembles the way nature assembles natural products, e.g. in polyketide synthase machinery. The application of lithiation-borylation chemistry to the synthesis of a broad variety of natural products is discussed in this Review.

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Section: Substrate-controlled Homologation Of Boronic Estersmentioning

confidence: 99%

Lithiation–borylation methodology in the total synthesis of natural products

2022

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“…The classical preparation of organoboranes utilizes reactions of a tricoordinate trialkoxyborane or trihaloborane with a Grignard or an organolithium reagent . Both reactants and the product are sensitive to moisture, while hydrolytically stable chiral boronic esters exhibit great convenience in practical storage and use. The most common strategy for the preparation of hydrolytically stable boronic esters involves the conversion of tricoordinate unstable boranes to a tetracoordinate complex stabilized by an N→B bond .…”

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Hydrolytically Stable Tricoordinate Chiral Bicyclo[4.4.0]diboronic Ester: Synthesis, Structural Characterization, and Theoretical Investigation

et al. 2006

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The hydrolytically and thermally stable tricoordinate chiral bicyclo[4.4.0] diboronic ester (R,R)-3c was synthesized via a one-step reaction of a Grignard reagent with chiral spiroborate esters (R,R,S)-1 and (R,R)-2. Its structure was characterized by its IR, 1H, 13C, and 11B NMR, and mass spectra and confirmed by X-ray analysis. Further theoretical investigation of the three possible bicyclic structures corresponding to the formula C40H32B2O4 was performed at different levels of theory. Excellent agreement with the X-ray result was obtained.

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1,2‐Metallate Rearrangement of Boron Derivatives

Bateman

Aggarwal

2019

Patai's Chemistry of Functional Groups

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The 1,2‐metallate rearrangement of boronate complexes has proven to be a powerful method for the stereospecific formation of CC and Cheteroatom bonds to generate molecules with a rich array of functionality with full stereocontrol. The enantioselectivity of the process is dictated by either incorporating a chiral ligand into the boronic ester component (substrate control) or by forming a boronate complex through the addition of an enantioenriched carbenoid species to a boronic ester (reagent control). A limitation of a substrate‐controlled process is that a two‐step procedure to exchange the enantiomer of chiral ligand must be performed to obtain the opposite diastereoisomer of product. In contrast, a reagent‐controlled process can access either enantiomer/diastereoisomer of product by altering the enantiomer of chiral reagent employed. This chapter will describe key advances in the substrate‐ and reagent‐controlled homologation of boronic esters, with a specific focus on the 1,2‐metallate rearrangement.

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Directed asymmetric synthesis with boronic esters

Cited by 10 publications

References 33 publications

Lithiation–borylation methodology in the total synthesis of natural products

Lithiation–borylation methodology in the total synthesis of natural products

Hydrolytically Stable Tricoordinate Chiral Bicyclo[4.4.0]diboronic Ester: Synthesis, Structural Characterization, and Theoretical Investigation

1,2‐Metallate Rearrangement of Boron Derivatives

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