@article {27346,
	title = {PSYCHEDELIC COMPOUNDS, METHODS OF THEIR PREPARATION AND USESTHEREOF},
	journal = {USA Provisional},
	number = {(Patent)},
	year = {2024},
	pages = {P-623813-USP},
	author = {Ahmad Masarwa and Avi PRIEL and Rami YAKA}
}
@article {27240,
	title = {Desymmetrization of Diboron (4) by a Trifluorination B-Masking Strategy: Practical Synthesis of Unsymmetrical Diboron Species},
	journal = {ChemRxiv},
	year = {2024},
	pages = {Submitted},
	url = {https://chemrxiv.org/engage/chemrxiv/article-details/65c9ef18e9ebbb4db9297afe},
	author = {Nadim Eghbarieh and Ahmad Masarwa*}
}
@article {27099,
	title = {PolyBorylated Alkenes as Energy-Transfer Reactive Groups: Access to Multi-Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event},
	journal = { Angewandte Chemie International Edition},
	year = {2024},
	note = {An earlier version of this paper was posted to ChemRxiv:https://chemrxiv.org/engage/chemrxiv/article-details/65461f2ba8b423585aed278d},
	pages = {e202405898},
	url = {https://onlinelibrary.wiley.com/doi/10.1002/anie.202405898},
	author = {Nicole Hanania and Nadim Eghbarieh and Ahmad Masrawa*}
}
@article {27072,
	title = {Stereoselective C\&minus;B and C\&minus;H Bonds Functionalization of polyBorylated Alkenes},
	journal = {ChemRxiv},
	year = {2024},
	pages = {Under Revisions},
	url = {https://chemrxiv.org/engage/chemrxiv/article-details/64f4775179853bbd78ff18e1},
	author = {Narendra K. Vaishanv and Nadim Eghbarieh and Rahul A. Jagtap and Ahmad Masarwa*}
}
@article {27025,
	title = {Synthesis and Functionalization of Thiophosphonium Salts: A Divergent Approach to Access Thioether, Thioester, and Dithioester Derivatives},
	journal = {Organic Letters},
	volume = {25},
	year = {2023},
	note = {\&nbsp;Most read Organic Letters publication for August 2023!\&nbsp;Early version of this manuscript was posted in ChemRxiv:Hazra, G. ; Masarwa*, A. Practical Synthesis and Functionalization of Thiophosphonium Salts: A Divergent Approach to Access Thioether, Thioester, and Dithioester Derivatives. ChemRxiv 2023\&nbsp;},
	pages = {6396-6400},
	url = {https://pubs.acs.org/doi/10.1021/acs.orglett.3c02422},
	author = {Gurupada Hazra and Ahmad Masarwa*}
}
@article {27013,
	title = {Interview with Ahmad Masarwa: This Young Career Focus presents Ahmad Masarwa (The Hebrew University of Jerusalem, Israel).},
	journal = {Synform  DOI: 10.1055/s-0040-1720600},
	volume = {2023/7},
	year = {2023},
	pages = { A116{\textendash}A119},
	url = {https://www.thieme.de/en/thieme-chemistry/synform-interview-with-ahmad-masarwa-173003.htm}
}
@article {26925,
	title = {Stereodefined polyMetalloid Alkenes Synthesis via Stereoselective Boron-Masking of polyBorylated Alkenes},
	journal = {Nature Communications },
	volume = {14},
	year = {2023},
	note = {Early version of this manuscript was posted in ChemRxiv:Stereoselective Boron-Masking of polyBorylated-Alkenes: An Access to Stereodefined polyMetalloid Alkeneshttps://chemrxiv.org/engage/chemrxiv/article-details/636ce76181f223065693d661},
	pages = {2022},
	url = {https://rdcu.be/c9A5p},
	author = {Nadim Eghbarieh and Nicole Hanania and Ahmad Masarwa*}
}
@article {26807,
	title = {A Triple Coupling to Make Alkynes.},
	journal = {Nature Synthesis},
	year = {2023},
	note = {\&nbsp;News \&amp; Views, Invited},
	url = {https://www.nature.com/articles/s44160-023-00257-y},
	author = {Nadim Eghbarieh and Ahmad Masarwa*}
}
@article {26697,
	title = {A Stereodivergent Approach to the Synthesis of gem-Diborylcyclopropanes},
	journal = {Chemistry{\textemdash}A European Journal},
	year = {2022},
	note = {Selected as Hot Paper },
	pages = {e202202748},
	url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202202748},
	author = {Nicole Hanania and Molhm Nassir and Nadim Eghbarieh and Ahmad Masarwa*}
}
@article {26087,
	title = {Photoredox-Mediated Deoxygenative Radical Additions of Aromatic Acids to Vinyl Boronic Esters and gem-Diborylalkenes},
	journal = {Chemistry{\textemdash}A European Journal},
	year = {2022},
	note = {Selected as Hot Paper Top Downloaded Article: This paper was one of the most downloaded during its 1rst 12 months of publication\&nbsp;},
	pages = {e202202646},
	url = {https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/chem.202202646},
	author = {Nagaraju Anugula and Tamer Saiaede and Nadim Eghbarieh and Ahmad Masrawa*}
}
@article {25417,
	title = {Sequential Selective C\&ndash;H and C(sp3)\&ndash;+P Bond functionalizations: An Entry to Bioactive Arylated Scaffolds.},
	journal = { Angewandte Chemie International Edition.},
	volume = {60},
	year = {2021},
	note = {Top Downloaded Article: This paper was one of the most downloaded during its 1rst 12 months of publication},
	pages = {26199{\textendash}26209 },
	abstract = {Organophosphonium salts containing C(sp3){\textendash}+P bonds are among the most utilized reagents in organic synthesis for constructing C{\textendash}C double bonds. However, their use as C-selective electrophilic groups is rare. Here, we explore an efficient and general transition-metal-free method for sequential chemo- and regioselective C{\textendash}H and C(sp3){\textendash}+P bond functionalizations. In the present study, C{\textendash}H alkylation resulting in the synthesis of benzhydryl triarylphosphonium salts was achieved by one-pot, four-component, cross-coupling reactions of simple and commercially available starting materials. The utility of the resulting phosphonium salt building blocks was demonstrated by the chemoselective post-functionalization of benzylic C(sp3){\textendash}+PPh3 groups to achieve aminations, thiolations, and arylations. In this way, Anchorbenzhydrylamines, benzhydrylthioethers, and triarylmethanes, structural motifs which feature in many pharmaceuticals and agrochemicals, are readily accessed. These include the synthesis of two anti-cancer agents from simple materials in only two to three steps. Additionally, a protocol for late-stage functionalization of bioactive drugs has been developed using benzhydrylphosphonium salts. This new approach should provide novel transformations for application in both academic and pharmaceutical research.[[{"fid":"29130","view_mode":"default","type":"media","attributes":{"height":"184","width":"767","alt":"angew","class":"media-element file-default"}}]]\&nbsp;},
	url = {https://onlinelibrary.wiley.com/doi/10.1002/anie.202111164},
	author = {K. Naresh Babu and Fedaa Massarwe and Israa Shioukhi and Ahmad Masarwa*}
}
@article {25354,
	title = {Stereoselective Diels-Alder Reactions of gem-Diborylalkenes: Toward the Synthesis of gem-Diboron-Based Polymers},
	journal = {Journal of the American Chemical Society},
	volume = {143},
	number = {143},
	year = {2021},
	note = {Nadim Eghbarieh and Nicole Hanania contributed equally to the work.},
	pages = {6211-6220},
	abstract = {Although gem-diborylalkenes are known to be among the most valuable reagents in modern organic synthesis, providing a rapid access to a wide array of transformations, including the construction of C-C and C-heteroatom bonds, their use as dienophile-reactive groups has been rare. Herein we report the Diels-Alder (DA) reaction of (unsymmetrical) gem-diborylalkenes. These reactions provide a general and efficient method for the stereoselective conversion of gem-diborylalkenes to rapidly access 1,1-bisborylcyclohexenes. Using the same DA reaction manifold with borylated-dienes and gem-diborylalkenes, we also developed a concise, highly regioselective synthesis of 1,1,2-tris- and 1,1,3,4-tetrakis(boronates)cyclohexenes, a family of compounds that currently lack efficient synthetic access. Furthermore, DFT calculations provided insight into the underlying factors that control the chemo-, regio, and stereoselectivity of these DA reactions. This method also provides stereodivergent syntheses of gem-diboryl-norbornenes. The utility of the gem-diboryl-norbornene building blocks was demonstrated by ring-opening metathesis polymerization (ROMP), providing a highly modular approach to the first synthesis of the gem-diboron-based polymers. Additionally, these polymers have been successfully submitted to post-polymerization modification reactions. Given its simplicity and versatility, we believe that this novel DA and ROMP approach holds great promise for organoboron synthesis as well as organoboron-based polymers and that it will result in more novel transformations in both academic and industrial research.[[{"fid":"28219","view_mode":"default","type":"media","attributes":{"height":"404","width":"510","style":"float: left;","alt":"toc jacs","class":"media-element file-default"}}]]},
	url = {https://pubs.acs.org/doi/10.1021/jacs.1c01471},
	author = {Nadim Eghbarieh and Nicole Hanania and Alon Zamir and Molhm Nassir and Stein, Tamar and Ahmad Masarwa*}
}
@article {24227,
	title = {Unsymmetrical 1,1-Bisboryl Species: Valuable Building Blocks in Synthesis},
	journal = {Molecules },
	volume = {25},
	year = {2020},
	note = {Invited Review  This article belongs to the Special Issue New Insights in Diversity Oriented Synthesis},
	pages = {959},
	abstract = {Unsymmetrical 1,1-bis(boryl)alkanes and alkenes are organo-bismetallic equivalents, which are synthetically important because they allow for sequential selective transformations of C{\textendash}B bonds. We reviewed the synthesis and chemical reactivity of 1,1-bis(boryl)alkanes and alkenes to provide information for the synthetic community. In the first part of this review, we disclose the synthesis and chemical reactivity of unsymmetrical 1,1-bisborylalkanes. In the second part, we describe the synthesis and chemical reactivity of unsymmetrical 1,1-bis(boryl)alkenes.\&nbsp;[[{"fid":26772,"view_mode":"default","type":"media","attributes":{"height":"838","width":"719","alt":"MOLECULES1","class":"media-element file-default"}}]]\&nbsp;},
	url = {https://www.mdpi.com/1420-3049/25/4/959},
	author = {K. Naresh Babu and Fedaa Massarwe and Reddy Rajasekhar Reddy and Nadim Eghbarieh and Manuella Jakob and Ahmad Masarwa*}
}
@article {24209,
	title = {Photoredox-Mediated Reaction of gem-Diborylalkenes: ReactivityToward Diverse 1,1-Bisborylalkanes},
	journal = {Chemistry{\textemdash}A European Journal},
	volume = {26},
	year = {2020},
	month = {2020},
	pages = {5360},
	abstract = {The use of gem-diborylalkenes as light-reactive groups is explored for the first time. These reactions provide an efficient and general method for the photochemical conversion of gem-diborylalkenes to rapidly access 1,1-bisborylalkanes. This method exploits a novel photoredox decarboxylative radical addition to gem-diborylalkenes to afford α-gemdiboryl carbon-centered radicals, which benefit from additional stability by virtue of an interaction with the empty p-orbitals on borons. The reaction offers a highly modular and regioselective approach to γ-amino gem-diborylalkanes. Furthermore, EPR spectroscopy and DFT calculations have provided insight into the radical mechanism underlying the photochemistry reaction.[[{"fid":"26443","view_mode":"default","type":"media","attributes":{"height":"563","width":"1000","alt":"DDDD","class":"media-element file-default"}}]]},
	url = {https://onlinelibrary.wiley.com/doi/10.1002/chem.202000603},
	author = {Nivesh Kumar and Nadim Eghbarieh and Stein, Tamar and Alexander I. Shames and Ahmad Masarwa*}
}
@article {24145,
	title = {α-Borylalkyl Radicals: Their Distinctive Reactivity in Modern Organic Synthesis},
	journal = {Chemical Communications},
	number = {56},
	year = {2020},
	note = {(Invited Review), the paper has been chosen for inclusion in an Editor{\textquoteright}s Choice collection.\&nbsp; i.e. specially curated collection on {\textquotedblleft}Organic Synthesis{\textquotedblright}. rsc.li/CCOrganic_Synthesis},
	pages = {13-25},
	abstract = {Organoborons are extremely important for synthetic organic chemistry; they can serve as advanced intermediates for a variety of transformations. Such a well-known transformation involves the loss of the boron moiety, creating alkyl radicals. Although these originally developed protocols for alkyl radical generation remain in active use today, in recent years their α-boryl carbon-centred radicles have been joined by a new array of radical generation strategies that offer a unique reactivity to forge a wider diversity of organoborones that often operate under mild and benign conditions. Herein, we will highlight the stability and reactivity of α-borylalkyl radicals and their remarkably recent advances in order to further utilise them for C{\textendash}C and C{\textendash}heteroatom bond formation. Their use for this purpose has been reported over the last decade in an attempt to guide the synthetic community. Various transition-metal and metal-free methods for their generation are presented, and more advanced photoredox approaches are discussed, mainly for the period of time 2009-2019.[[{"fid":26375,"view_mode":"default","type":"media","attributes":{"height":"563","width":"1000","alt":"chem 2","title":"VV","class":"media-element file-default"}}]]},
	url = {https://pubs.rsc.org/en/content/articlelanding/2019/cc/c9cc08027a},
	author = {Nivesh Kumar and Reddy Rajasekhar Reddy and Nadim Eghbarieh and Ahmad Masarwa*}
}
@article {23396,
	title = {Synthesis and Reactivity of 1,1 and 1,2-Bisboronate Species},
	journal = {(PATAI{\textquoteright}S Chemistry of Functional Groups) John Wiley \& Sons, Chichester, England     },
	year = {2020},
	note = {(Invited Book Chapter)},
	abstract = {In the past four decades, the chemistry of 1,1- and 1,2-bisboronate compounds has been extensively explored. Many interesting structural features and reaction patterns have emerged, and more importantly, these compounds now feature prominently in both metal-catalyzed and metal-free transformations for the formation of CC bonds and C{\textendash}heteroatom and other processes. This chapter aims to highlight the recent development in this rising research field, focusing on the synthesis of 1,1- and 1,2-bisboronate compounds and their reactivity and selectivity that originate from the use of these bisboronates.},
	url = {https://onlinelibrary.wiley.com/doi/full/10.1002/9780470682531.pat0975},
	author = {rajender nallagonda and Nivesh Kumar and Reddy Rajasekhar Reddy and Israa Shioukhi and Hila Sagih and Ahmad Masarwa*}
}
@article {23397,
	title = {Stereoselective Desymmetrization of gem-Diborylalkanes by \&ldquo;Trifluorination\&rdquo;},
	journal = {Chemistry {\textendash} A European Journal},
	volume = {25},
	year = {2019},
	note = {Selected as Hot Paper Has been recognized as one of the most read in Chemistry - A European Journal for the years 2018-2019! },
	pages = {8008-8012},
	abstract = {An efficient and general method for the chemoselective synthesis of unsymmetrical gem-diborylalkanes is reported. This method is based on a novel late-stage desymmetrization via nucleophilic {\textquotedblleft}trifluorination{\textquotedblright}, providing chiral gem-diborylalkanes bearing a trifluoroborate group. The reaction offers a highly modular and diastereoselective approach to synthesize gem-diborylcyclopropanes. The utility of the gem-diborylalkane building blocks was demonstrated by selective post-functionalization of the trifluoroborate group. These functionalizations include inter- and intra- Pd-catalyzed Suzuki-Miyaura coupling reactions.\&nbsp;                    },
	url = {https://onlinelibrary.wiley.com/doi/10.1002/chem.201901267},
	author = {Nivesh Kumar and Reddy Rajasekhar Reddy and Ahmad Masarwa*}
}
@article {21495,
	title = {gem-Diborylalkanes: recent advances in their preparation, transformation and application},
	journal = {Org. Biomol. Chem.},
	volume = {16},
	year = {2018},
	note = {(Invited Review)},
	pages = {1050 - 1064},
	abstract = {Recently, gem-diborylalkanes have attracted much attention as versatile building blocks and fundamental intermediates in organic synthesis, because they enable multiple C{\textendash}C bond construction and further transformation at C{\textendash}B bonds. Importantly, gem-diborylalkanes can be utilised as bisnucleophilic partners in a variety of chemo-selective C{\textendash}C bond-forming reactions. This review describes recent developments in synthesising gem-diborylalkanes in complex molecules along with their chemical transformation. In the first part of the review the different synthetic approaches used to synthesise gem-diborylalkanes are described. In the second part, an overview of the chemoselective transformation of gem-diborylalkanes into various functionalized materials is discussed along with one-carbon homologation of diborylmethane via a selective uni- and bidirectional method.[[{"fid":20433,"view_mode":"default","type":"media","attributes":{"height":"563","width":"1000","alt":"OBC","class":"media-element file-default"}}]]},
	url = {https://pubs.rsc.org/en/content/articlelanding/2018/OB/C7OB02978K$\#$!divAbstract},
	author = {rajender nallagonda and Kishor Padala and Ahmad Masarwa*}
}
@article {21488,
	title = {Zirconocene-Mediated Selective C-C Bond Cleavage of Strained Carbocycles: Scope and Mechanism},
	journal = {The Journal of Organic Chemistry},
	year = {2018},
	abstract = {Several approaches using organozirconocene species for the remote cleavage of strained three-membered ring carbocycles are described. -Ene polysubstituted cyclopropanes, alkylidenecyclopropanes, -ene spiro[2.2]pentanes and -ene cyclopropyl methyl ethers were successfully transformed into stereodefined organometallic intermediates allowing an easy access to highly stereoenriched acyclic scaffolds in good yields and in most cases excellent selectivities. DFT calculations and isotopic labeling experiments were performed to delineate the origin of the obtained chemo- and stereoselectivities, demonstrating the importance of microreversibility.[[{"fid":"20852","view_mode":"default","type":"media","attributes":{"height":"563","width":"1000","alt":"joc new","class":"media-element file-default"}}]]},
	url = {https://pubs.acs.org/doi/pdf/10.1021/acs.joc.7b03115},
	author = {Jeffrey Bruffaerts and Alexandre Vasseur and Sukhdev Singh and Ahmad Masarwa and Dorian Didier and Liron Oskar and Lionel Perrin* and Odile Eisenstein* and Ilan Marek*}
}
@article {7701,
	title = {Quinazoline-Based Tricyclic Compounds that Regulate Programmed Cell Death, Induce Neuronal Differentiation, and are Curative in Animal Models for Excitotoxicity and Hereditary Brain Disease},
	journal = {Cell Death Discovery},
	volume = {1},
	year = {2015},
	pages = {15027},
	abstract = {Expanding on a quinazoline scaffold, we developed tricyclic compounds with biological activity. These compounds bind to the 18 kDa translocator protein (TSPO) and protect U118MG (glioblastoma cell line of glial origin) cells from glutamate-induced cell death. Fascinating, they can induce neuronal differentiation of PC12 cells (cell line of pheochromocytoma origin with neuronal characteristics) known to display neuronal characteristics, including outgrowth of neurites, tubulin expression, and NeuN (antigen known as {\textquoteleft}neuronal nuclei{\textquoteright}, also known as Rbfox3) expression. As part of the neurodifferentiation process, they can amplify cell death induced by glutamate. Interestingly, the compound 2-phenylquinazolin-4-yl dimethylcarbamate (MGV-1) can induce expansive neurite sprouting on its own and also in synergy with nerve growth factor and with glutamate. Glycine is not required, indicating that N-methyl-D-aspartate receptors are not involved in this activity. These diverse effects on cells of glial origin and on cells with neuronal characteristics induced in culture by this one compound, MGV-1, as reported in this article, mimic the diverse events that take place during embryonic development of the brain (maintenance of glial integrity, differentiation of progenitor cells to mature neurons, and weeding out of non-differentiating progenitor cells). Such mechanisms are also important for protective, curative, and restorative processes that occur during and after brain injury and brain disease. Indeed, we found in a rat model of systemic kainic acid injection that MGV-1 can prevent seizures, counteract the process of ongoing brain damage, including edema, and restore behavior defects to normal patterns. Furthermore, in the R6-2 (transgenic mouse model for Huntington disease; Strain name: B6CBA-Tg(HDexon1)62Gpb/3J) transgenic mouse model for Huntington disease, derivatives of MGV-1 can increase lifespan by \&gt;20\% and reduce incidence of abnormal movements. Also in vitro, these derivatives were more effective than MGV-1.},
	url = {http://www.nature.com/articles/cddiscovery201527},
	author = {Alex Vainshtein and Leo Veenman and Alex Shterenberg and Sukhdev Singh and Ahmad Masarwa and Bishnu Dutta and Biana Island and Einav Tsoglin and Evgeny Levin and Svetlana Leschiner and Inbal Maniv and Lena Pe{\textquoteright}er and Irina Otradnov and Salman Zubedat and Shlomit Mizrachi and Abraham Weizman and Avi Avital and Ilan Marek and Moshe Gavish*}
}
@article {7699,
	title = {Selective Carbon-Carbon Bond Cleavage for the Stereoselective Synthesis of Acyclic Systems},
	journal = {Angew. Chem. Int. Ed.},
	volume = {54},
	year = {2015},
	pages = {414-429},
	abstract = {Most of the efforts of organic chemists have been directed to the development of creative strategies to build carbon{\textendash}carbon and carbon{\textendash}heteroatom bonds in a predictable and efficient manner. In this Review, we show an alternative approach where challenging molecular skeletons could be prepared through selective cleavage of carbon{\textendash}carbon bonds. We demonstrate that it has the potential to be a general principle in organic synthesis for the regio-, diastereo-, and even enantioselective preparation of adducts despite the fact that CC single bonds are among the least reactive functional groups. The development of such strategies may have an impact on synthesis design and can ultimately lead to new selective and efficient processes for the utilization of simple hydrocarbons.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/anie.201405067/full},
	author = {Ilan Marek* and Ahmad Masarwa and Pierre-Olivier Delaye and Markus Leibeling}
}
@article {7700,
	title = {Synthesis and Stereochemical Assignment of Crypto-Optically Active 2H6-Neopentane},
	journal = {Angew. Chem. Int. Ed.},
	volume = {54},
	year = {2015},
	pages = {13106{\textendash}13109 },
	abstract = {The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of 2H6-1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to 2H6-1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/anie.201505349/full},
	author = {Ahmad Masarwa and Dennis Gerbig and Liron Oskar and Aharon Loewenstein and Hans Peter Reisenauer and Philippe Lesot* and Peter R. Schreiner* and Ilan Marek*}
}
@article {7482,
	title = {Construction of Enantiopure Taxoid and Natural Products-Like Scaffolds Using a C-C Bond Cleavage/Arylation Reaction},
	journal = {Org. Lett.},
	volume = {17},
	year = {2015},
	pages = { 5432{\textendash}5435},
	abstract = {An approach to construct enantiopure complex natural product-like frameworks, including the first reported synthesis of a C17 oxygenated taxoid scaffold, is presented. A palladium-catalyzed C{\textendash}C activation/cross-coupling is utilized to access these structures in a short sequence from (+)-carvone; the scope of this reaction is explored.},
	url = {http://pubs.acs.org/doi/abs/10.1021/acs.orglett.5b02797},
	author = {Manuel Weber and Kyle Owens and Ahmad Masarwa* and Richmond Sarpong*}
}
@article {7481,
	title = {Selective C-C and C-H bond Activation/Cleavage of Pinene Derivatives: Synthesis Of Enantiopure Cyclohexanone Scaffolds and Mechanistic insights},
	journal = {J. Am. Chem. Soc.},
	volume = {137},
	year = {2015},
	pages = {6327-6334},
	abstract = {The continued development of transition-metal-mediated C-C bond activation/cleavage methods would provide even more opportunities to implement novel synthetic strategies. We have explored the Rh(I)-catalyzed C-C activation of cyclobutanols resident in hydroxylated derivatives of pinene, which proceed in a complementary manner to the C-C bond cleavage that we have observed with many traditional electrophilic reagents. Mechanistic and computational studies have provided insight into the role of C-H bond activation in the stereochemical outcome of the Rh-catalyzed C-C bond activation process. Using this new approach, functionalized cyclohexenones that form the cores of natural products, including the spiroindicumides and phomactin A, have been accessed.},
	url = {http://pubs.acs.org/action/doSearch?AllField=ahmad+masarwa\&type=within\&publication=40001010},
	author = {Ahmad Masarwa and Manuel Weber and Richmond Sarpong*}
}
@article {7483,
	title = {Merging Allylic Carbon-Hydrogen and Selective Carbon-Carbon bond Activation},
	journal = {Nature},
	volume = {505},
	year = {2014},
	pages = {199{\textendash}203},
	abstract = {
Article preview View full access options


Nature | Letter


Print
Share/bookmark




日本語要約

 
 


Merging allylic carbon{\textendash}hydrogen and selective carbon{\textendash}carbon bond activation

Ahmad Masarwa,
Dorian Didier,
Tamar Zabrodski,
Marvin Schinkel,
Lutz Ackermann
\&amp; Ilan Marek


Affiliations
Contributions
Corresponding author

Nature505,199{\textendash}203(09 January 2014)doi:10.1038/nature12761Received22 August 2013Accepted08 October 2013Published online08 December 2013

Article tools

Citation
Reprints
Rights \&amp; permissions
Article metrics



Since the nineteenth century, many synthetic organic chemists have focused on developing new strategies to regio-, diastereo- and enantioselectively build carbon{\textendash}carbon and carbon{\textendash}heteroatom bonds in a predictable and efficient manner1, 2, 3. Ideal syntheses should use the least number of synthetic steps, with few or no functional group transformations and by-products, and maximum atom efficiency. One potentially attractive method for the synthesis of molecular skeletons that are difficult to prepare would be through the selective activation of C{\textendash}H and C{\textendash}C bonds4, 5, 6, 7, 8, instead of the conventional construction of new C{\textendash}C bonds. Here we present an approach that exploits the multifold reactivity of easily accessible substrates9 with a single organometallic species to furnish complex molecular scaffolds through the merging of otherwise difficult transformations: allylic C{\textendash}H and selective C{\textendash}C bond activations10, 11, 12. The resulting bifunctional nucleophilic species, all of which have an all-carbon quaternary stereogenic centre, can then be selectively derivatized by the addition of two different electrophiles to obtain more complex molecular architecture from these easily available starting materials.
},
	url = {http://www.nature.com/nature/journal/v505/n7482/full/nature12761.html},
	author = {Ahmad Masarwa and Dorian Didier and Tamar Zabrodski and Marvin Schinkel and Lutz Ackermann and Ilan Marek*}
}
@article {7702,
	title = {selective in Metal-Catalyzed Carbon-Carbon Bond Cleavage of Alkylidenecyclopropanes},
	journal = {Chem. Eur. J.},
	volume = {16},
	year = {2010},
	pages = {9712{\textendash}9721},
	abstract = {When more complex system leads to simpler reactivity profile; the ring-opening of strained three-membered rings such as methylene- and alkylidenecyclopropanes generally lead to several products. If one starts with more functionalized carbon skeletons, selective reactions are now observed and rationalization as well as synthetic applications are described in this concept article. This methodology could be used to the preparation of challenging structural motifs possessing quaternary carbon stereocenters in acyclic systems.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/chem.201001246/full},
	author = {Ahmad Masarwa and Ilan Marek*}
}
@article {7703,
	title = {Cyclopropenylcarbinol Derivatives as New Versatile In Organic Synthesis: Application to the Formation of Enantiomerically Pure Alkylidenecyclopropane Derivatives},
	journal = {Chem. Eur. J.},
	volume = {15},
	year = {2009},
	pages = {8449{\textendash}8464},
	abstract = {The copper-catalyzed carbomagnesiation (or hydrometalation) reaction of chiral cyclopropenylcarbinol derivatives, obtained by means of a kinetic resolution of secondary allylic alcohols, leads to an easy and straightforward preparation of enantiomerically pure alkylidenecyclopropane derivatives. The reaction mechanism is composed of a syn-carbometalation followed by a syn-elimination reaction. To gain further insight into the reaction mechanism of the carbometalation, the diastereoselective formation of cyclopropylcarbinol was also achieved and was found to be very sensitive to the nature of the organometallic species used for the addition reaction. Cyclopropylcarbinol could also be prepared through a diastereoselective reduction of cyclopropenylcarbinol derivatives. Finally, functionalization of enantiomerically enriched cyclopropenylcarbinols into the corresponding acetate or phosphinite derivatives leads, under mild conditions, to various enantiomerically pure heterosubstituted alkylidenecyclopropanes.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/chem.200901074/full},
	author = {Samah Simaan and Ahmad Masarwa and Elinor Zohar and Amnon Stanger and Philippe Bertus and Ilan Marek*}
}
@article {7494,
	title = {Metal-Catalyzed Rearrangement of enantiomerically Pure Alkylidenecyclopropane Derivatives as a New access to Cyclobutenes Possessing Quaternary stereocenters},
	journal = {Chem. Commun.},
	year = {2009},
	pages = {5760-5762},
	abstract = {Pd(II)- and Pt(II)-catalyzed ring-expansion of enantiomerically pure alkylidenecyclopropane derivatives leads to the formation of cyclobutene species with a complete preservation of the stereogenic center.},
	url = {http://pubs.rsc.org/en/Content/ArticleLanding/2009/CC/b910465h$\#$!divAbstract},
	author = {Ahmad Masarwa and Alois F{\"u}rstnerb and Ilan Marek*}
}
@article {7698,
	title = {Enantiomerically Enriched Cyclopropene Derivatives: Versatile Building Blocks in Asymmetric Synthesis},
	journal = {Angew. Chem. Int. Ed.},
	volume = {46},
	year = {2008},
	pages = {7364{\textendash}7376},
	abstract = {Enantiomerically enriched cyclopropene derivatives, the smallest possible unsaturated carbocycles, are of great synthetic interest since they serve as versatile reactive building blocks. Their reactivity results from the relief of the ring strain in the small molecule. They can be transformed into a wide variety of complex chiral structures and a special emphasis will be directed towards the preparation of enantiomerically enriched methylene- and alkylidenecyclopropane derivatives. The ready availability of a wide range of these chiral entities now provides an excellent opportunity to discover new and unique transformations that can further enrich mainstream synthetic methodology.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/anie.200604774/full},
	author = {Ilan Marek* and Samah Simaan and Ahmad Masarwa}
}
@article {7697,
	title = {An Efficient , Facial, and General Stereoselective Synthesis of Heterosubstituted Alkylidenecyclopropanes},
	journal = {Angew. Chem., Int. Ed.},
	volume = {46},
	year = {2007},
	pages = {8039-8042},
	abstract = {With just a nudge (in the form of silica gel, an acidic ion-exchange resin, or heating at about 40 {\textdegree}C), the acetate derivatives of enantiomerically enriched cyclopropenyl alcohols undergo sigmatropic rearrangement to give alkylidenecyclopropanes with high ee  values (see scheme). Similarly, the rearrangement of phosphinite derivatives at room temperature leads to phosphine oxide precursors of unusual chiral phosphine ligands. R1, R2=alkyl, aryl.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/anie.200702713/full},
	author = {Ahmad Masarwa and Amnon Stanger and Ilan Marek*}
}
@article {7696,
	title = {Enantiomercally Pure Cyclopropeneylecarbenols as a Source of Chiral Alkylidenecyclopropane Derivatives},
	journal = {Angew. Chem., Int. Ed. },
	volume = {45},
	year = {2006},
	pages = {3963-3965},
	abstract = {The straightforward approach: The copper-catalyzed carbomagnesiation reaction of chiral cyclopropenylcarbinol derivatives, obtained through kinetic resolution of secondary allylic alcohols, leads to the preparation of enantiomerically pure alkylidenecyclopropane derivatives. The reaction mechanism is composed of a syn carbometalation followed by a syn elimination reaction.},
	url = {http://onlinelibrary.wiley.com/doi/10.1002/anie.200600556/full},
	author = {Samah Simaan and Ahmad Masarwa and Philippe Bertus and Ilan Marek*}
}
