Publications

These papers have been cited ≥620 times and 14 of these papers have been cited at least 14 times (H-Index).

016	Pheromone Chemistry High-Performance Liquid Chromatography Quantification of Enantiomers of a Dihydroxylated Tetrahydrofuran Natural Product Ke Li, Skye D Fissette, Tyler J Buchinger, Zoe E Middleton, Alistair Boyer, Weiming Li* Chirality, 2018, online DOI: 10.1002/chir.22978 Our synthesis [see below] of the marine natural product petromyroxol enabled this novel method for detecting natural product enantiomers as a valuable technique for studying pheromones. Both enantiomers of petromyroxol are putative pheromones in sea lamprey (Petromyzon marinus). Here, we describe the separation and quantification of the petromyroxol enantiomers using high-performance liquid chromatography tandem mass spectrometry. The separation was tested on a wide range of chiral columns with normal phases, and effects of the chromatographic parameters such as mobile phase and temperature on the separation were optimized. The AD-H column showed the best separation of enantiomers with n-hexane and ethanol as the mobile phase. The enantiomers were detected by multiple reaction monitoring with a positive atmospheric-pressure chemical ionization on triple quadrupole mass spectrometer. Validation revealed that the method was specific, accurate, and precise. The validated method was applied to measure the amount of petromyroxol enantiomers in water conditioned with sea lamprey larvae, the source of the putative pheromone. This method will be applied in quantifying the natural scalemic petromyroxol mixture, enabling further investigations of a rare non-racemic enantiomeric pheromone mixture in a vertebrate species.
015	Total Synthesis: Oxonium Ylide Formation and Rearrangement of 1-Sulfonyl-1,2,3-Triazoles Enantioselective Synthesis of (+)-Petromyroxol, Enabled by Rhodium-Catalyzed Denitrogenation and Rearrangement of a 1-Sulfonyl-1,2,3-Triazole Alistair Boyer J. Org. Chem, 2015, 80, 4771–4775 DOI: 10.1021/acs.joc.5b00399 This work was built on the reactivity of β-allyloxy 5-substituted triazoles [see below]. This work enabled the development of a novel HPLC detection method [see above] as a valuable technique for studying pheromones. The excellent photo of the sea lamprey was taken by Ted Lawrence, Great Lakes Fishery Commission [link]. This work has been cited: 17 times. Petromyroxol is a non-racemic mixture of enantiomeric oxylipids isolated from water conditioned with larval sea lamprey. The (+)-antipode exhibits interesting biological properties but only 1 mg was isolated from >100000 L of water. Recently, transition metal-catalyzed denitrogenation of 1-sulfonyl-1,2,3-triazoles has emerged as a powerful strategy for the synthesis of value-added products, including efficient diastereocontrolled construction of tetrahydrofurans. This methodology enabled the rapid development of the first synthesis of (+)-petromyroxol in 9 steps and 20% overall yield from a readily accessible starting material.
014	Brønsted Acid Catalysis: Cyclopropanation Synthesis of Cyclopropyl-Substituted Furans by Brønsted Acid Promoted Cascade Reactions J Stephen Clark, Filippo Romiti, Kirsten F Hogg, Malai Haniti S A Hamid, Sven C Richter, Alistair Boyer, Joanna C Redman and Louis J Farrugia Angew. Chem. Int. Ed., 2015, 54, 5744–5747 DOI: 10.1002/anie.201500625 This work complements the sulfur-catalysed formation of furfuryl alcohols, esters and amines from ynenones [see below]. ISI Hot Paper 2015 This work has been cited: 20 times. Chloroacetic acid promotes an efficient and diastereoselective intramolecular cascade reaction of electron-deficient ynenones to deliver products featuring a 2,3,5-trisubstituted furan bearing a fused cyclopropyl substituent at the 5-position. Synthetically relevant polycyclic building blocks featuring various size rings and heteroatoms have been synthesized in high yield using this mild acid-catalysed reaction.
013	1-Sulfonyl-1,2,3-Triazoles: Oxonium Ylide Formation and Rearrangement Rhodium(II)-Catalyzed Stereocontrolled Synthesis of 2-Tetrasubstituted Saturated Heterocycles from 1-Sulfonyl-1,2,3-triazoles Alistair Boyer Org. Lett., 2014, 16, 5878–5881 DOI: 10.1021/ol5028267 This work was inspired by the reativity of isomeric 5-substituted triazoles which undergo an analogous rearrangement to give dihydrofuran-3-ones [see below]. This work has been cited: 39 times. Rhodium(II) acetate catalyzes the denitrogenative transformation of 4-substituted 1-sulfonyl-1,2,3-triazoles with pendent allyl and propargyl ethers and thioethers to onium ylides that undergo [2,3]-sigmatropic rearrangement to give 2-tetrasubstituted heterocycles with high yield and diastereoselectivity.
012	1-Sulfonyl-1,2,3-Triazoles: Oxonium Ylide Formation and Rearrangement Rhodium(II)-Catalyzed Stereocontrolled Synthesis of Dihydrofuran-3-imines from 1-Tosyl-1,2,3-Triazoles Alistair Boyer Org. Lett., 2014, 16, 1660–1663 DOI: 10.1021/ol500309x Isomeric 4-substituted triazoles undergo an analogous rearrangement to give 2-tetrasubstituted saturated heterocycles [see above]. This method enabled a rapid synthesis of the marine natural product petromyroxol [see above]. ISI Highly Cited Paper 2014, 2015 Highlighted on the organic-chemistry.org portal [Link] Awarded the Dave Kelly Cup for presentation of this research at the 2013 Gregynog Synthesis Workshop This work has been cited: 64 times. Rhodium(II) acetate catalyzes the denitrogenative transformation of 5-substituted and 4,5-disubstituted 1-sulfonyl-1,2,3-triazoles with pendent allyl and propargyl ether motifs to oxonium ylides that undergo [2,3]-sigmatropic rearrangement to give substituted dihydrofuran-3-imines in high yield and diastereoselectivity.
011	Organocatalysis: Sulfur Catalysis Organocatalytic Synthesis of Highly Substituted Furfuryl Alcohols and Amines J Stephen Clark, Alistair Boyer, Anthony Aimon, Paloma Engel García, David M Lindsay, Andrew D F Symington, Yves Danoy Angew. Chem. Int. Ed., 2012, 51, 12128–12131 DOI: 10.1002/anie.201207300 This work complements the Brønsted acid-catalysed formation of cyclopropyl-substituted furans from ynenones [see above]. Invited presentation at the COST Action Meeting (CM0804), Izmir, Turkey Invited presentation at the 2012 RSC Perkin Meeting, St. Andrews, UK Highlighted as part of the Wiley Organocatalysis Hot Topic [Link] Highlighted in SynFacts [Abstract] This work has been cited: 40 times. Tetrahydrothiophene (THT) is an efficient organocatalyst for the synthesis of highly substituted furfuryl products from readily-accessible electron-poor enynes under neutral conditions. This process is demonstrated to be applicable to a wide-range of nucleophiles and enynes; and can be incorporated in a domino organocatalysis sequence.
010	Rhodium Catalysis: Domino Reactions Rhodium-Catalysed Domino Enantioselective Synthesis of Bicyclo[2.2.2]lactones Alistair Boyer, Mark Lautens Angew. Chem. Int. Ed., 2011, 50, 7346–7349 DOI: 10.1002/anie.201101773 Featured in ChemInform 2011, 42 [Link] This work was presented at the 2011 CSC Chemistry Conference, Montreal, Canada [Abstract] This work has been cited: 25 times. Once... twice... three times a catalyst! We demonstrate a novel triple domino rhodium(I)-catalysed asymmetric transformation of substituted oxabicyclic alkenes into bicycle[2.2.2]lactones. The reaction proceeds with good yields and excellent levels of stereoselectivity in each of the 16 examples studied. Mechanistic investigations suggest that this process proceeds by rhodium catalysed asymmetric ring opening, allylic alcohol isomerisation and oxidation.
009	Rhodium Catalysis: Regiodivergent Resolution Practical Asymmetric Synthesis of Bioactive Aminotetralins from a Racemic Precursor using a Regiodivergent Resolution Robert Webster, Alistair Boyer, Matthew J Fleming, Mark Lautens Org. Lett., 2010, 12, 5418–5421 DOI: 10.1021/ol1022239 Highlighted in SynFacts [Link] This work has been cited: 43 times. Catalyst-controlled asymmetric ring opening of a racemic oxabicyclic alkene leads to two readily separable regioisomeric products both in excellent ee. A cationic Rh catalyst, with added NH₄BF₄ to modulate reactivity, was required to obtain synthetically useful yields. The utility of each substituted aminotetralin product has been demonstrated by their conversion to different biologically relevant molecules in a highly efficient and practical manner.
008	Rhodium Catalysis: Domino Reactions Domino Rhodium(I)-Catalysed Reactions for the Efficient Synthesis of Substituted Benzofurans and Indoles Alistair Boyer, Naohiro Isono, Sebastian Lackner, Mark Lautens Tetrahedron, 2010, 66, 6468–6482 DOI: 10.1016/j.tet.2010.05.106 Invited contribution in honour of Prof. Steven V. Ley's receipt of the 2009 Tetrahedron Prize This work was presented at the 2010 CSC Chemistry Conference, Toronto, Canada Featured in ChemInform [Link] This work has been cited: 59 times. Rhodium(I) catalysts promote the transformation of o-alkynyl phenols and anilines to the corresponding benzo[b]furans and indoles. The reaction is postulated to proceed via a transient 3-rhodium heterocycle intermediate, which can be trapped with suitable electrophiles to give poly-substituted heterocycles. In the case of mono-substituted electron-withdrawn electrophiles, excellent yield and selectivity for conjugate addition versus Heck/Mizoroki reaction can be achieved. In the case of 2-alkynyl pyridine electrophiles, novel 2-(benzofuran-3-yl)vinylpyridines are formed.
007	Total Synthesis: Azadirachtin Second-Generation Synthesis of Azadirachtin: A Concise Preparation of the Propargylic Mesylate Fragment Alistair Boyer, Gemma E Veitch, Edith Beckmann, Steven V Ley Angew. Chem. Int. Ed., 2009, 48, 1317–1320 DOI: 10.1002/anie.200805395 Read the original communications, review and full paper, also see our synthesis of related natural products Highlighted in "Classics in Total Synthesis III" [Link] This work was presented at the 2007 ACS Chemistry Conference, Boston, USA [ORGN-121] This work has been cited: 17 times. A second bite of the apple: A new and highly efficient synthesis of the propargylic mesylate fragment of azadirachtin has been accomplished. An enantioselective catalytic hetero Diels-Alder reaction sets up the stereocenter at C15, which then controls the installation of the remaining functionality in a total of only 17 steps.
006	Total Synthesis: Azadirachtin The Azadirachtin Story Gemma E Veitch, Alistair Boyer, Steven V Ley Angew. Chem. Int. Ed., 2008, 47, 9402–9429 DOI: 10.1002/anie.200802675 Read the original communications and full paper and also see our second generation approach and our synthesis of related natural products Highlighted in "Classics in Total Synthesis III" [Link] Featured in ChemInform [Link] This work has been cited: 53 times. Azadirachtin has been the subject of intensive research within the scientific community ever since its isolation from the neem tree in 1968. There are now over 1000 publications relating to this natural product which cover all aspects of structural, biological and synthetic studies. Herein, we describe the worldwide efforts towards the synthesis of this fascinating molecule.	cover by Matt O'Brien
005	Total Synthesis: Azadirachtin The Synthesis of Azadirachtin: A Potent Insect Antifeedant Steven V Ley, et al. (show all...) Chem. Eur. J., 2008, 14, 10683–10704 DOI: 10.1002/chem.200801103 Read the original communications and review and also see our second generation approach and our synthesis of related natural products VIP paper Highlighted in "Classics in Total Synthesis III" [Link] This work has been cited: 38 times. The final chapter! We describe in full the first synthesis of the potent insect antifeedant azadirachtin through a highly convergent approach. An O-alkylation reaction is used to unite decalin ketone and propargylic mesylate fragments, after which a Claisen rearrangement constructs the central C8-C14 bond in a stereoselective fashion. The allene which results from this sequence then enables a second critical carbon-carbon bond forming event whereby the [3.2.1] bicyclic system, present in the natural product, is generated via a 5-exo-radical cyclisation process. Finally, using knowledge gained through our early studies into the reactivity of the natural product, a series of carefully designed steps completes the synthesis of this challenging molecule.	cover by Alistair Boyer
004	Supercritical Carbon Dioxide Clean and Efficient Synthesis of O-Silylcarbamates and Ureas in Supercritical Carbon Dioxide Matthew J Fuchter, Catherine J Smith, Melanie W S Tsang, Alistair Boyer, Simon Saubern, John H Ryan, Andrew B Holmes Chem. Commun., 2008, 2152–2154 DOI: 10.1039/b801537f Featured in ChemInform [Link] This work has been cited: 26 times. The synthesis of a family of O-silylcarbamates from the corresponding silylamines has been achieved simply by heating the silylamine in supercritical carbon dioxide (scCO2), and these O-silylcarbamates have been shown to be effective precursors for the synthesis of a range of symmetrical and unsymmetrical ureas.
003	Total Synthesis: Azadirachtin Synthesis of Natural Products from the Indian Neem Tree Azadirachta Indica Gemma E Veitch, Andrea Pinto, Alistair Boyer, Edith Beckmann, James C Anderson, Steven V Ley Org. Lett., 2008, 10, 569–572 DOI: 10.1021/ol7027898 Read the original communications, review and full paper and also see our second generation approach Highlighted in "Classics in Total Synthesis III" [Link] This work has been cited: 14 times. The synthesis of five natural products isolated from the Indian neem tree Azadirachta indica, is reported from a common intermediate. The judicious choice of transacetalization conditions allows efficient access to both the azadirachtinin and the azadirachtin skeletons.
002	Total Synthesis: Azadirachtin A Relay Route for the Synthesis of Azadirachtin Gemma E Veitch, Edith Beckmann, Brenda J Burke, Alistair Boyer, Carles Ayats, Steven V Ley Angew. Chem. Int. Ed., 2007, 46, 7633–7635 DOI: 10.1002/anie.200703028 Read our review and full paper and also see our second generation approach and our synthesis of related natural products Back-to-back publication [see below] VIP paper Featured in "Classics in Total Synthesis III" [Link] Featured in ChemInform [Link] This work has been cited: 53 times. 22 Years in the making: Azadirachtin was synthesized for the first time by a highly convergent approach, utilizing a Claisen rearrangement and a radical cyclization as key steps. End-game strategies relied on a relay-intermediate, which could be obtained by synthetic methods as well as by degradation of the natural product.	cover by Alistair Boyer
001	Total Synthesis: Azadirachtin Synthesis of Azadirachtin: A Long but Successful Journey Gemma E Veitch, Edith Beckmann, Brenda J Burke, Alistair Boyer, Sarah Maslen, Steven V Ley Angew. Chem. Int. Ed., 2007, 46, 7629–7632 DOI: 10.1002/anie.200703027 Read our review and full paper and also see our second generation approach and our synthesis of related natural products Back-to-back publication [see above] VIP paper Highlighted in "Classics in Total Synthesis III" [Link] SynFact of the Month [Link] Featured in Chemistry World [Link] Featured in Chemical and Engineering News [Link] Featured in an Angewandte Chemie Highlight [Link] Featured in Nature [Link] Featured in ChemInform [Link] This work has been cited: 107 times. 22 Years in the making: Azadirachtin was synthesized for the first time by a highly convergent approach, utilizing a Claisen rearrangement and a radical cyclization as key steps. End-game strategies relied on a relay-intermediate, which could be obtained by synthetic methods as well as by degradation of the natural product.	cover by Alistair Boyer
Non-refereed contributions:
002	Organic Syntheses Preparation of Horner-Wadsworth-Emmons Reagent: Methyl 2-Benzyloxycarbonylamino-2-(dimethoxyphosphinyl)-acetate Submitters: Hiroki Azuma, Kentaro Okano, Tohru Fukuyama, Hidetoshi Tokuyama Checkers: Alistair Boyer, Mark Lautens Org. Synth., 2011, 88, 152–161 DOI: 10.15227/orgsyn.088.0152
001	Organic Syntheses Synthesis of Substituted Indazoles via [3+2] Cycloaddition of Benzyne and Diazo Compounds Submitters: Feng Shi, Richard C Larock Checkers: Alistair Boyer, Mark Lautens Org. Synth., 2010, 87, 95–103 DOI: 10.15227/orgsyn.087.0095 This work has been cited: 5 times. Benzyne is a highly reactive intermediate that has attracted wide attention from synthetic organic chemists. One of the commercially available precursors of benzyne is 2-(trimethylsilyl)phenyl trifluoromethanesulfonate which undergoes fluoride-promoted ortho-elimination to generate benzyne, mild conditions which tolerate a range of functional groups. Benzyne which is generated in this way has been shown to react with diazo compounds as 1,3-dipoles to afford substituted 1H-indazoles following a hydrogen shift.

Publications

Non-refereed contributions: