Parallel Synthesis of Terminal Alkynes Using a ROMPgel-Supported Ethyl 1-Diazo-2-oxopropylphosphonate

Barrett, Anthony G. M.; Hopkins, Brian T.; Love, and Andrew C.; Tedeschi, Livio

doi:10.1021/ol049915z

Cited by 41 publications

(22 citation statements)

References 18 publications

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“…[27][28][29][30][31] Barrett et al actively developed ROMP-gel supported reagents using this methodology, and reported many excellent immobilized reagents. 4,9,[32][33][34] These reagents have several advantages in addition to high-loading, e.g., high tolerance of the methathesis catalysts for diverse functionalities, and readily available monomers from inexpensive precursors. Recently, ROMP supported coupling reagents carrying fluoroformamidinium or 2-bromopyridinium were also reported.…”

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confidence: 99%

Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

et al. 2007

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The advance in combinatorial chemistry has resulted in the development of solid-supported reagents that can be applied to automated synthesis of a target molecule. As a result, many useful reagents that are well established in the field of solution-phase chemistry have been applied to immobilized reagents. [1][2][3][4][5][6][7][8][9] There have been some recent reports on the preparation of immobilized reagents for dehydrocondensation.10-18) However, since most of these reagents are immobilized by connecting dehydrocondensing reagents to insoluble carriers such as polystyrene and silica gel, they would be prepared by inefficient chemical transformation on the insoluble carrier under heterogeneous conditions. In addition, the weight proportion of the solid carrier relative to the amount of solidsupported reagent is generally high, which inevitably results in the generation of large amounts of waste; this is a serious problem common to solid-supported reagents. To resolve this issue, we developed a new immobilized triazine-type dehydrocondensing reagent by polymerizing the dehydrocondensing reagent itself.19) This polymer reagent is based on the condensing agent, 4,6-dimethoxy-1,3,5-triazinyl-2-methylmorpholinium chloride (DMT-MM) [20][21][22][23][24][25][26] and is a crosslinked polymer prepared by co-polymerizing tetra(ethylene glycol) bis(4-chloro-6-methoxy-1,3,5-triazin-2-yl) ether and tris(2-aminoethyl)amine, which is easily substituted onto the triazine ring under weakly basic conditions.In this work, we developed another application for polymer-type triazine condensing reagents: immobilization by well-established ROMP (ring opening metathesis polymerization) method, in which the reaction proceeds rapidly and with high yield under mild neutral conditions. The dramatically expanded ROMP methodology, based on the work of Grubbs et al. in the 1990s, has been developed as an effective method for acquiring high-loading polymer reagents by polymerizing the reagent unit as a monomer.27-31) Barrett et al. actively developed ROMP-gel supported reagents using this methodology, and reported many excellent immobilized reagents. 4,9,[32][33][34] These reagents have several advantages in addition to high-loading, e.g., high tolerance of the methathesis catalysts for diverse functionalities, and readily available monomers from inexpensive precursors. Recently, ROMP supported coupling reagents carrying fluoroformamidinium or 2-bromopyridinium were also reported.11) In this case, however, preparation of the monomers, which requires operation of 3-4 steps, seems not to be very easy.Our monomer 1a was readily prepared by reacting cyanuric chloride consecutively with 5-norbornene-2-methanol and MeOH (Chart 1). A CH 2 Cl 2 solution of the resulting monomer and cross-linker 2 35) in a mixing ratio of p : q, as shown in Table 1, was allowed to react in the presence of 0.1 mol% Grubbs' catalyst 3 to produce four kinds of polymer with cross-linking percentages of 10, 30, 50 and 100%. The polymer reagents exhibited condensation activ...

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Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

et al. 2007

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“…BOX ligands were prepared as described in the literature. 21 Alkynes 6j , 22 6q , 23 6r , 24 6s , 25 6v , 26 6w , 27 and 6x 28 were prepared as described in the literature.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Copper-Catalyzed Alkynylation of Benzopyranyl Oxocarbenium Ions

et al. 2015

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We have developed highly enantioselective, copper-catalyzed alkynylations of benzopyranyl acetals. By using a copper(I) catalyst equipped with a chiral bis(oxazoline) ligand, high yields and enantioselectivities are achieved in the alkynylation of widely available, racemic isochroman and chromene acetals to deliver α-chiral oxygen heterocycles. This method demonstrates that chiral organometallic nucleophiles can be successfully used in enantioselective additions to oxocarbenium ions.

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“…87 A new enantioselective synthesis of both (2R)-OMPT (173) and (2S)-OMPT (174) has been described (Scheme 49). It was shown that esters (182) are as fully active as natural LPA ( Figure 32). Similar results were found for calcium release, MAPK and Akt activation, and IL-6 release in human OVCAR 3 ovarian cancer cell.…”

Section: Scheme 41mentioning

confidence: 98%

“…86 A novel series of phosphate esters (170), (171) and (172), small molecule tags with high affinity for serum albumin, reduce clearance and increase the circulating half life of bioactive peptides administered to rabbits ( Figure 27) ( Figure 28). 92 A new and efficient route to enantiomerically homogenous lysophospholipid analogues from (S)-1,2,4-butanetriol (181) has given two 3-difluoromethyl substituted analogues of 2-acyl-sn-glycerol-3-phosphate (182). Calcium release assays in both LPA 3transfected insect Sf9 and rat hapatoma Rh 7777 cells showed that (2S)-OMPT was 5-to 20-fold more active than (2R)-OMPT.…”

Section: Scheme 41mentioning

confidence: 99%

Organophosphorus Chemistry

Hall

Bricklebank

Grampel³

et al. 2006

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Organophosphorus compounds are ubiquitous in nature, and due to their innate chemical properties, serve a fundamental role in a number of important fields. Among the more prominent features that elevate their status as a unique and versatile class of compounds, include variable oxidation states, multivalency, asymmetry and metal-binding properties. Their presence in bioactive natural products, endogenous biomolecules, small molecule therapeutic agents and pro-drugs substantiates their role in modern synthetic chemistry and chemical biology. Moreover, their central use as ligands and effectors in asymmetric catalysis, as well as key functional groups for the development of new synthetic methods, has taken the field to new heights. This Thematic Series highlights and details some of the novel methods that are advancing the field of organophosphorus chemistry.The Thematic Series covers topics that range from new synthetic methods and phosphorus-based ligands in asymmetric catalysis to bisphosphonates as promising enzyme inhibitors. More specifically, the Thematic Series spans new methods in C-P bond formation, chiral phosphines in nucleophilic organocatalysis, chiral N-phosphinyl auxiliaries, cyclic phosphonamide reagents in the total synthesis of natural products, phosphinate-containing heterocycles, new routes to phosphinoyl-indoles and phosphinoyl-isocoumarins and new chemistries of H-phosphonates. The Thematic Series also details work on new metathesis-based reactions of vinyl phosphonates and phosphate tethers, novel phosphorus-based ligands in asymmetric catalysis, novel rasta resin-triphenylphosphine oxides and their use as recyclable heterogeneous reagents, the Atherton-Todd reaction, cyclic phosphonium ionic liquids with distinct properties, photo-removable phosphate protecting groups, new methods of C-H functionalization using phosphoryl-related directing groups, the exciting chemistry of substituted phosphanylidenecarbenes and phosphoryl azides, and bisphosphonate ethers as promising inhibitors of geranylgeranyl diphosphate synthase (GGDPS).The articles and reviews capture the emerging potential of organophosphorus compounds and exciting opportunities in the field, and hopefully, will inspire and motivate investigators in the field to investigate new chemistry in this area. Taken collectively, organophosphorus chemistry embodies a broad, vibrant and continual growing scientific area with this Thematic Series highlighting recent advances in the field. We are grateful and indebted to the authors for their hard work and exciting contri-

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Parallel Synthesis of Terminal Alkynes Using a ROMPgel-Supported Ethyl 1-Diazo-2-oxopropylphosphonate

Cited by 41 publications

References 18 publications

Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

Immobilized Triazine-Type Dehydrocondensing Reagents for Carboxamide Formation: ROMP-Trz-Cl and ROMP(OH)-Trz-Cl

Enantioselective Copper-Catalyzed Alkynylation of Benzopyranyl Oxocarbenium Ions

Organophosphorus Chemistry

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