General Method for Synthesis of 2-Heterocyclic <i>N</i>-Methyliminodiacetic Acid Boronates

Dick, Graham R.; Knapp, David M.; Gillis, Eric P.; Burke, Martin D.

doi:10.1021/ol100671v

Cited by 113 publications

(59 citation statements)

References 57 publications

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“…10,11,12,13,14,15,16,17,18,19,20,21,22,23,24 MIDA boronates have many desirable properties that render them exceptionally useful as synthetic intermediates. They are uniformly air-stable, non-toxic, highly crystalline, and monomeric free-flowing solids that are fully compatible with silica gel chromatography.…”

Section: Introductionmentioning

confidence: 99%

“…They are uniformly air-stable, non-toxic, highly crystalline, and monomeric free-flowing solids that are fully compatible with silica gel chromatography. Many methods now exist for preparing MIDA boronates from a wide range of different starting materials, including boronic acids, 10,11,12,13,19,25 haloboranes, 11,13 boronic esters, 16 trialkoxyborate salts, 14–17,19 organohalides, 19 organolithium reagents, 19,23 and Grignard reagents. 15,16 The MIDA boronate functional group is inert to anhydrous cross-coupling conditions, yet can be readily transformed into a fully reactive boronic acid or ester using mild conditions.…”

Section: Introductionmentioning

confidence: 99%

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(1-Bromovinyl)-MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

2013

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

(1-Bromovinyl)-MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

2013

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“…[94,96,97] This methodology is also suitable to couple highly unstable boronic acids, since reactive boronic acid species can be slowly released during the reaction from the typically stable, crystalline MIDA boronate form. [98–101] …”

Section: One Machine – Many Small Moleculesmentioning

confidence: 99%

The Molecular Industrial Revolution: Automated Synthesis of Small Molecules

2018

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The eighteenth and nineteenth centuries marked a sweeping transition from manual to automated manufacturing on the macroscopic scale. This enabled an unmatched period of human innovation that helped drive the Industrial Revolution. The impact on society was transformative, ultimately yielding substantial improvements in living conditions and lifespan in many parts of the world. During the same time period, the first manual syntheses of organic molecules was achieved. Now, two centuries later, we are poised for an analogous transition from highly customized crafting of specific molecular targets by hand to the increasingly general and automated assembly of many different types of molecules with the push of a button. Automation of customized small molecule synthesis pathways is already enabling safer, more reproducible, and readily scalable production of specific targets, and general machines now exist for the synthesis of a wide range of different peptides, oligonucleotides, and oligosaccharides. Creating general machines that are similarly capable of making many different types of small molecules on-demand, akin to that which has been achieved on the macroscopic scale with 3D printers, has proven to be substantially more challenging. Yet important progress is being made toward this potentially transformative objective with two complementary approaches: (1) automation of customized synthesis routes to different targets via machines that enable use of many different reactions and starting materials, and (2) automation of generalized platforms that make many different targets using common coupling chemistry and building blocks. Continued progress in these exciting directions has the potential to shift the bottleneck in molecular innovation from synthesis to imagination, and thereby help drive a new industrial revolution on the molecular scale.

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“…2-Pyridinylboronic acids and esters using halogen-metal exchange (HMe) are generally synthesized from 2-bromopyridines (3, X = 2-Br). 5,6,13,17,[34][35][36][37][38][39][40][41][42] In the particular case of compound 3 (X = 2-I), 2-iodopyridine was used. 16 To improve the stability (particularly in air and water), pyridine-2-boronates such as 6, 34 7, 35,36 and 8 37,38 were developed.…”

Section: The Synthesis Of Pyridinylboronic Acids and Esters By Halogementioning

confidence: 99%

Recent progress in the synthesis of pyridinylboronic acids and esters

Liu¹,

Milo²,

Lai

2013

Arkivoc

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Recent progress in the synthesis of (un)substituted pyridinylboronic acids and esters is reviewed. Five approaches to the synthesis of (un)substituted pyridinylboronic acids and esters are summarized: (1) halogen-metal exchange (HMe) and borylation, (2) metal-hydrogen exchange via directed ortho-metallation (DoM) followed by borylation, (3) palladium-catalyzed crosscoupling of halopyridines with tetraalkoxydiborane or dialkoxyhydroborane (4) iridium or rhodium catalyzed C-H or C-F borylation, and (5) exchange / borylation 2.1.1. The general procedure of halogen-metal (Li or Mg) exchange / borylation 2.1.2. The selectivity of halogen-metal (Li or Mg) exchange / borylation 2.1.3. The synthesis of 2-pyridinylboronic acids and esters by halogen-organometal (Li or Mg) exchange / borylation 2.1.4. The synthesis of pyridinediboronic acids via halogen-organotin (Sn) exchange / borylation 2.2. The synthesis of pyridinylboronic acids and esters by directed ortho-metalation (DoM) / borylation 2.2.1. The general procedure of directed ortho-metalation (DoM) / borylation 2.2.2. The selectivity of directed ortho-metalation (DoM) / borylation 2.3. The synthesis of pyridinylboronic acids and esters by palladium-catalyzed cross-coupling of halopyridines with tetraalkoxydiboron or dialkoxyhydroborane 2.4. The synthesis of pyridinylboronic acids and esters by iridium-or rhodium-catalyzed

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General Method for Synthesis of 2-Heterocyclic N-Methyliminodiacetic Acid Boronates

Abstract: A wide range of 2-pyridyl and other difficult-to-access heterocyclic N-methyliminodiacetic acid boronates can be readily prepared from the corresponding bromides via a new method involving direct transligation of trialkoxyborate salts with MIDA at elevated temperatures.

Cited by 113 publications

References 57 publications

(1-Bromovinyl)-MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

(1-Bromovinyl)-MIDA boronate: a readily accessible and highly versatile building block for small molecule synthesis

The Molecular Industrial Revolution: Automated Synthesis of Small Molecules

Recent progress in the synthesis of pyridinylboronic acids and esters

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