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However, the practical use of silylenes as useful silicon synthons remains limited, as specific stabilizing substituents are currently required in order to suppress self-condensation and oligomerization. Herein, we report a novel strategy to generate diversely substituted silylenes through a reaction with an electron-deficient aryllithium to form boron-ate silylenoids derived from isolable chlorosilylborane precursors. Several chlorosilylboranes were readily prepared via the Si\u2013H borylation of dialkylanisylsilanes and subsequent chlorination of the anisyl group, or via the monoborylation of dihydrosilanes followed by chlorination of the remaining hydride group. The generated silylenes exhibit the inherent reactivity associated with free silylenes, i.e., \u03c3-insertions into Si\u2013H bonds and \u03c0-additions to alkene and carbonyl compounds. Mechanistic studies revealed that the concentrations of the lithium silylenoid and the subsequent silylene remained lower than that of the boron-ate silylenoid due to the thermodynamic and kinetic unfavorability of the boron\u2013lithium exchange. As a result of the low concentration of the generated silylene, it selectively reacts with the silylene acceptor rather than participating in side reactions such as self-condensation and oligomerization, which are problematic in the reduction of dichlorosilanes. Consequently, this work represents a reliable strategy to harness silylenes as versatile silicon synthons for transformations that are difficult to realize via the more conventional alkali-metal-mediated reduction of dihalosilanes.<\/jats:p>","DOI":"10.1021\/jacs.6c05205","type":"journal-article","created":{"date-parts":[[2026,8,20]],"date-time":"2026-08-20T10:01:36Z","timestamp":1787220096000},"page":"36519-36529","source":"Crossref","is-referenced-by-count":0,"title":["A Complementary\nApproach to Dialkylsilylenes via Thermodynamically\nStable Boron-Ate Silylenoids Derived from Chlorosilylboranes"],"prefix":"10.1021","volume":"148","author":[{"given":"Rikuro","family":"Takahashi","sequence":"first","affiliation":[{"name":"Hokkaido University , , , ,","place":["Sapporo, Hokkaido, Japan, 060-8628"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ryohei","family":"Yamaguchi","sequence":"additional","affiliation":[{"name":"Hokkaido University , , , ,","place":["Sapporo, Hokkaido, Japan, 060-8628"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3852-6721","authenticated-orcid":true,"given":"Hajime","family":"Ito","sequence":"additional","affiliation":[{"name":"Hokkaido University , , , ,","place":["Sapporo, Hokkaido, Japan, 060-8628"]},{"name":"Hokkaido University , , , ,","place":["Sapporo, Hokkaido, Japan, 001-0021"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,20]]},"reference":[{"issue":"13","key":"2026090312072555700_cit1","doi-asserted-by":"publisher","first-page":"3438","DOI":"10.1021\/ja01015a028","article-title":"The Thermolysis of Methoxypolysilanes","volume":"90","author":"Atwell","year":"1968","journal-title":"J. Am. Chem. Soc."},{"issue":"4","key":"2026090312072555700_cit2","doi-asserted-by":"publisher","first-page":"989","DOI":"10.1039\/C5CS00365B","article-title":"Group 14 Inorganic\nHydrocarbon Analogues","volume":"45","author":"Rivard","year":"2016","journal-title":"Chem. Soc. Rev."},{"issue":"26","key":"2026090312072555700_cit3","doi-asserted-by":"publisher","first-page":"6476","DOI":"10.1039\/C9SC01192G","article-title":"A Vinyl Silylsilylene\nand Its Activation of Strong Homo- and Heteroatomic Bonds","volume":"10","author":"Roy","year":"2019","journal-title":"Chem. Sci."},{"issue":"30","key":"2026090312072555700_cit4","doi-asserted-by":"publisher","first-page":"9628","DOI":"10.1021\/ja062928i","article-title":"A New Type of N-Heterocyclic\nSilylene with Ambivalent Reactivity","volume":"128","author":"Driess","year":"2006","journal-title":"J. Am.\nChem. Soc."},{"issue":"9","key":"2026090312072555700_cit5","doi-asserted-by":"publisher","first-page":"2866","DOI":"10.1002\/chem.200903019","article-title":"Stable N-Heterocyclic\nCarbene Adducts of Arylchlorosilylenes and Their Germanium Homologues","volume":"16","author":"Filippou","year":"2010","journal-title":"Chem. Eur. J."},{"issue":"49","key":"2026090312072555700_cit6","doi-asserted-by":"publisher","first-page":"11276","DOI":"10.1002\/chem.202001062","article-title":"N-Heterocyclic\nSilylenes as Ligands in Transition Metal Carbonyl Chemistry: Nature\nof Their Bonding and Supposed Innocence","volume":"26","author":"Krahfu\u00df","year":"2020","journal-title":"Chem.\nEur. J."},{"issue":"18","key":"2026090312072555700_cit7","doi-asserted-by":"publisher","first-page":"6733","DOI":"10.1039\/D0CS00815J","article-title":"Where Silylene-Silicon Centres Matter in the Activation\nof Small Molecules","volume":"49","author":"Shan","year":"2020","journal-title":"Chem. Soc. Rev."},{"issue":"5","key":"2026090312072555700_cit8","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202114485","article-title":"Synthesis\nand Reactivity\nof a Neutral Homocyclic Silylene","volume":"61","author":"Keuter","year":"2022","journal-title":"Angew. Chem.,\nInt. Ed"},{"issue":"214413","key":"2026090312072555700_cit9","doi-asserted-by":"publisher","first-page":"214413","DOI":"10.1016\/j.ccr.2022.214413","article-title":"Isolable Silylenes and Their Diverse\nReactivity","volume":"457","author":"Wang","year":"2022","journal-title":"Coord. Chem. Rev."},{"issue":"6","key":"2026090312072555700_cit10","doi-asserted-by":"publisher","first-page":"2691","DOI":"10.1021\/ja00085a088","article-title":"Synthesis\nand Structure of a Stable Silylene","volume":"116","author":"Denk","year":"1994","journal-title":"J. Am. Chem.\nSoc."},{"issue":"16","key":"2026090312072555700_cit11","doi-asserted-by":"publisher","first-page":"2405","DOI":"10.1039\/dt9940002405","article-title":"Electronic Structure\nof a Stable Silylene: Photoelectron Spectra and Theoretical Calculations\nof Si(NRCHCHNR), Si(NRCH2CH2NR) and SiH2(NRCHCHNR)","author":"Denk","year":"1994","journal-title":"J. Chem. Soc., Dalton Trans."},{"issue":"41","key":"2026090312072555700_cit12","doi-asserted-by":"publisher","first-page":"9722","DOI":"10.1021\/ja9925305","article-title":"The First Isolable\nDialkylsilylene","volume":"121","author":"Kira","year":"1999","journal-title":"J. Am. Chem. Soc."},{"issue":"50","key":"2026090312072555700_cit13","doi-asserted-by":"publisher","first-page":"15554","DOI":"10.1002\/anie.201608736","article-title":"A Two-Coordinate\nCyclic (Alkyl)(Amino)Silylene:\nBalancing Thermal Stability and Reactivity","volume":"55","author":"Kosai","year":"2016","journal-title":"Angew. Chem., Int. Ed."},{"issue":"2","key":"2026090312072555700_cit14","doi-asserted-by":"publisher","first-page":"568","DOI":"10.1002\/anie.201208554","article-title":"A Generic One-Pot Route to Acyclic\nTwo-Coordinate Silylenes from Silicon(IV) Precursors: Synthesis and\nStructural Characterization of a Silylsilylene","volume":"52","author":"Protchenko","year":"2013","journal-title":"Angew. Chem., Int. Ed."},{"issue":"2","key":"2026090312072555700_cit15","doi-asserted-by":"publisher","first-page":"164","DOI":"10.1002\/anie.198601641","article-title":"Decamethylsilicocene\u2500Synthesis\nand Structure","volume":"25","author":"Jutzi","year":"1986","journal-title":"Angew. Chem., Int. 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Chem."},{"issue":"1","key":"2026090312072555700_cit18","doi-asserted-by":"publisher","first-page":"11","DOI":"10.1016\/S0010-8545(00)00315-5","article-title":"Lithiosilanes\nand Their Application\nto the Synthesis of Polysilane Dendrimers","volume":"210","author":"Sekiguchi","year":"2000","journal-title":"Coord.\nChem. Rev."},{"issue":"1","key":"2026090312072555700_cit19","doi-asserted-by":"publisher","first-page":"57","DOI":"10.1016\/S0022-328X(01)00745-8","article-title":"Silylene R*XSi (R*=SitBu3; X = H,\nMe, Ph, Hal, R*):\nBildung und Reaktionen","volume":"628","author":"Wiberg","year":"2001","journal-title":"J. Organomet. Chem."},{"issue":"2","key":"2026090312072555700_cit20","doi-asserted-by":"publisher","first-page":"377","DOI":"10.1002\/chem.200305151","article-title":"Syntheses and Reactivities of Stable\nHalosilylenoids, (Tsi)X2SiLi (Tsi = C(SiMe3)3, X = Br, Cl)","volume":"10","author":"Lee","year":"2004","journal-title":"Chem. Eur. J."},{"issue":"9","key":"2026090312072555700_cit21","doi-asserted-by":"publisher","first-page":"2784","DOI":"10.1021\/ja0575880","article-title":"Synthesis Molecular Structure, and\nReactivity of the Isolable Silylenoid with a Tricoordinate Silicon","volume":"128","author":"Molev","year":"2006","journal-title":"J. Am. Chem. Soc."},{"issue":"15","key":"2026090312072555700_cit22","doi-asserted-by":"publisher","first-page":"5227","DOI":"10.1021\/om3005349","article-title":"A New Synthetic\nRoute for Silacyclopropanes: Reactions\nof a Bromosilylenoid with Olefins","volume":"31","author":"Cho","year":"2012","journal-title":"Organometallics"},{"issue":"7","key":"2026090312072555700_cit23","doi-asserted-by":"publisher","first-page":"469","DOI":"10.1002\/anie.196904691","article-title":"Divalent\nSilicon Intermediates","volume":"8","author":"Atwell","year":"1969","journal-title":"Angew. Chem., Int. Ed."},{"issue":"10","key":"2026090312072555700_cit24","doi-asserted-by":"publisher","first-page":"1355","DOI":"10.1002\/anie.198813551","article-title":"Convenient Routes to Di-Tert-butylsilanediyl:\nChemical, Thermal and Photochemical Generation","volume":"27","author":"Boudjouk","year":"1988","journal-title":"Angew. Chem., Int. Ed."},{"issue":"5","key":"2026090312072555700_cit25","doi-asserted-by":"publisher","first-page":"398","DOI":"10.1002\/hc.1060","article-title":"Characterization,\nand Photoreactions of 1,2-Disiladigermacyclobutane","volume":"12","author":"Hashimoto","year":"2001","journal-title":"Heteroat. Chem."},{"issue":"13","key":"2026090312072555700_cit26","doi-asserted-by":"publisher","first-page":"3235","DOI":"10.1021\/om500485m","article-title":"En Route to\nStable All-Carbon-Substituted\nSilylenes: Synthesis and Reactivity of a Bis(\u03b1-Spirocyclopropyl)Silylene","volume":"33","author":"Redies","year":"2014","journal-title":"Organometallics"},{"issue":"23","key":"2026090312072555700_cit27","doi-asserted-by":"publisher","first-page":"6524","DOI":"10.1021\/ja020183k","article-title":"Diastereoselective\nSilacyclopropanations\nof Functionalized Chiral Alkenes","volume":"124","author":"Driver","year":"2002","journal-title":"J. Am. Chem.\nSoc."},{"issue":"35","key":"2026090312072555700_cit28","doi-asserted-by":"publisher","first-page":"10659","DOI":"10.1021\/ja0301370","article-title":"Mechanism of Di-Tert-Butylsilylene Transfer from a\nSilacyclopropane to an Alkene","volume":"125","author":"Driver","year":"2003","journal-title":"J. Am. Chem.\nSoc."},{"issue":"12","key":"2026090312072555700_cit29","doi-asserted-by":"publisher","first-page":"4007","DOI":"10.1021\/jo0355505","article-title":"Metal-Catalyzed Di-Tert-Butylsilylene\nTransfer: Synthesis and Reactivity of Silacyclopropanes","volume":"69","author":"C\u0301irakovic\u030c","year":"2004","journal-title":"J. Org. Chem."},{"issue":"31","key":"2026090312072555700_cit30","doi-asserted-by":"publisher","first-page":"9522","DOI":"10.1021\/ja047498f","article-title":"Formation and Utility\nof Oxasilacyclopentenes Derived\nfrom Functionalized Alkynes","volume":"126","author":"Clark","year":"2004","journal-title":"J. Am. Chem. Soc."},{"issue":"32","key":"2026090312072555700_cit31","doi-asserted-by":"publisher","first-page":"9993","DOI":"10.1021\/ja0306563","article-title":"Mechanism\nof Silver-Mediated Di-Tert-Butylsilylene\nTransfer from a Silacyclopropane to an Alkene","volume":"126","author":"Driver","year":"2004","journal-title":"J. Am. Chem. Soc."},{"issue":"7","key":"2026090312072555700_cit32","doi-asserted-by":"publisher","first-page":"2046","DOI":"10.1021\/ja042893r","article-title":"Silylene Transfer\nto Carbonyl Compounds and Subsequent\nIreland-Claisen Rearrangements to Control Formation of Quaternary\nCarbon Stereocenters","volume":"127","author":"Calad","year":"2005","journal-title":"J. Am. Chem. Soc."},{"issue":"19","key":"2026090312072555700_cit33","doi-asserted-by":"publisher","first-page":"3773","DOI":"10.1021\/ol701424a","article-title":"Metal-Catalyzed\nSilylene Transfer to Imines: Synthesis\nand Reactivity of Silaaziridines","volume":"9","author":"Neva\u0301rez","year":"2007","journal-title":"Org. Lett."},{"issue":"42","key":"2026090312072555700_cit34","doi-asserted-by":"publisher","first-page":"12602","DOI":"10.1021\/ja073758s","article-title":"Metal-Catalyzed Silylene Insertions\nof Allylic Ethers: Stereoselective Formation of Chiral Allylic Silanes","volume":"129","author":"Bourque","year":"2007","journal-title":"J. Am. Chem. Soc."},{"issue":"22","key":"2026090312072555700_cit35","doi-asserted-by":"publisher","first-page":"5257","DOI":"10.1021\/ol8018538","article-title":"Intermolecular Silacarbonyl\nYlide Cycloadditions: A\nDirect Pathway to Oxasilacyclopentenes","volume":"10","author":"Bourque","year":"2008","journal-title":"Org.\nLett."},{"issue":"28","key":"2026090312072555700_cit36","doi-asserted-by":"publisher","first-page":"5608","DOI":"10.1016\/j.tet.2009.04.016","article-title":"Silylene Oxonium\nYlides: Di-Tert-Butylsilylene Insertion into C-O Bonds","volume":"65","author":"Bourque","year":"2009","journal-title":"Tetrahedron"},{"issue":"33","key":"2026090312072555700_cit37","doi-asserted-by":"publisher","first-page":"6447","DOI":"10.1016\/j.tet.2009.05.066","article-title":"Silylene Transfer\nto Alpha-Keto Esters and Application\nto the Synthesis of Gamma-Lactones","volume":"65","author":"Howard","year":"2009","journal-title":"Tetrahedron"},{"issue":"18","key":"2026090312072555700_cit38","doi-asserted-by":"publisher","first-page":"7180","DOI":"10.1021\/jo901111j","article-title":"Silylene-Mediated Ring Contraction\nof Homoallylic Ethers to Form Allylic Silanes","volume":"74","author":"Bourque","year":"2009","journal-title":"J. Org. Chem."},{"issue":"40","key":"2026090312072555700_cit39","doi-asserted-by":"publisher","first-page":"14182","DOI":"10.1021\/ja906204a","article-title":"Insertions of Silylenes\ninto Vinyl Epoxides: Diastereoselective\nSynthesis of Functionalized, Optically Active Trans-Dioxasilacyclooctenes","volume":"131","author":"Pre\u0301vost","year":"2009","journal-title":"J. Am. Chem. Soc."},{"issue":"16","key":"2026090312072555700_cit40","doi-asserted-by":"publisher","first-page":"5729","DOI":"10.1021\/jo1008228","article-title":"Silylene Transfer\nto Allylic Sulfides: Formation of Substituted Silacyclobutanes","volume":"75","author":"Ager","year":"2010","journal-title":"J. Org. Chem."},{"issue":"39","key":"2026090312072555700_cit41","doi-asserted-by":"publisher","first-page":"9275","DOI":"10.1039\/c003227a","article-title":"Strained\nOrganosilacyclic Compounds:\nSynthesis of Anti-Bredt Olefins and Trans-Dioxasilacyclooctenes","volume":"39","author":"Pre\u0301vost","year":"2010","journal-title":"Dalton Trans."},{"issue":"3","key":"2026090312072555700_cit42","doi-asserted-by":"publisher","first-page":"406","DOI":"10.1021\/ja109631z","article-title":"Silylene-Mediated\nPolarity Reversal of Dienoates: Additions\nof Dienoates to Aldehydes at the \u03b4-Position to Form Trans-Dioxasilacyclononenes","volume":"133","author":"Ventocilla","year":"2011","journal-title":"J. Am. Chem. Soc."},{"issue":"30","key":"2026090312072555700_cit43","doi-asserted-by":"publisher","first-page":"12482","DOI":"10.1021\/ja305713v","article-title":"Diastereoselective\nSynthesis of Seven-Membered-Ring Trans-Alkenes from Dienes and Aldehydes\nby Silylene Transfer","volume":"134","author":"Greene","year":"2012","journal-title":"J. Am. Chem. Soc."},{"issue":"49","key":"2026090312072555700_cit44","doi-asserted-by":"publisher","first-page":"13033","DOI":"10.1002\/anie.201306093","article-title":"Diastereoselective Synthesis of Eight-Membered-Ring\nAllenes from Propargylic Epoxides and Aldehydes by Silylene Insertion\ninto Carbon-Oxygen Bonds","volume":"52","author":"Rotsides","year":"2013","journal-title":"Angew. Chem., Int.\nEd."},{"issue":"27","key":"2026090312072555700_cit45","doi-asserted-by":"publisher","first-page":"8763","DOI":"10.1039\/C6DT04612F","article-title":"Diastereoselective Silylene Transfer Reactions to Chiral\nEnantiopure Alkenes: Effects of Ligand Size and Substrate Bias","volume":"46","author":"Rotsides","year":"2017","journal-title":"Dalton Trans."},{"issue":"5","key":"2026090312072555700_cit46","doi-asserted-by":"publisher","first-page":"1526","DOI":"10.1021\/ja073896h","article-title":"Silylboranes\nBearing Dialkylamino\nGroups on Silicon as Silylene Equivalents: Palladium-Catalyzed Regioselective\nSynthesis of 2,4-Disubstituted Siloles","volume":"130","author":"Ohmura","year":"2008","journal-title":"J. Am.\nChem. Soc."},{"issue":"46","key":"2026090312072555700_cit47","doi-asserted-by":"publisher","first-page":"16624","DOI":"10.1021\/ja907170p","article-title":"Palladium-Catalyzed\nSilylene-13-Diene [4 + 1] Cycloaddition with Use of (Aminosilyl)Boronic\nEsters as Synthetic Equivalents of Silylene","volume":"131","author":"Ohmura","year":"2009","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026090312072555700_cit48","doi-asserted-by":"publisher","first-page":"1322","DOI":"10.1021\/om200135u","article-title":"2-Vinylindoles\nAs the Four-Atom Component\nin a Catalytic [4 + 1] Cycloaddition with a Silylene-Palladium Species\nGenerated from (Aminosilyl)Boronic Ester","volume":"30","author":"Masuda","year":"2011","journal-title":"Organometallics"},{"issue":"6","key":"2026090312072555700_cit49","doi-asserted-by":"publisher","first-page":"1649","DOI":"10.1021\/acs.orglett.9b00326","article-title":"Catalytic\nGeneration of Rhodium Silylenoid\nfor Alkene-Alkyne-Silylene [2 + 2 + 1] Cycloaddition","volume":"21","author":"Ohmura","year":"2019","journal-title":"Org. 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