Conjugate Hydrostannation of Unsaturated Esters by Iodotin Hydride Ate Complex

Shibata, Ikuya; Suwa, Toshihiro; Ryu, Kyoichiro; Baba, Akio

doi:10.1021/jo016081e

Cited by 19 publications

(7 citation statements)

References 10 publications

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“…Yellowish oil; 56% yield. NMR spectra were identical to the reported data . Compound 27 was isolated as a 10:1 mixture with methyl 3-(4-chlorophenyl)acrylate.…”

Section: Methodssupporting

confidence: 66%

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Ti/Ni-Mediated Inter- and Intramolecular Conjugate Addition of Aryl and Alkenyl Halides and Triflates

et al. 2014

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In this work, we show that the unique combination of a nickel catalyst and Cp2TiCl allows the direct conjugate addition of aryl and alkenyl iodides, bromides, and to a lesser extent, chlorides and triflates to α,β-unsaturated carbonyls at room temperature, without requiring the previous formation of an organometallic nucleophile. The reaction proceeds inter- and intramolecularly with good functional group compatibility, which is key for the development of free protecting group methodologies. Carbo- and heterocycles of five- and six-membered rings are obtained in good yields. Moreover, some insights about the mechanism involved have been obtained from cyclic voltammetry, UV-vis, and HRTEM measurements.

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“…Yellowish oil; 56% yield. NMR spectra were identical to the reported data . Compound 27 was isolated as a 10:1 mixture with methyl 3-(4-chlorophenyl)acrylate.…”

Section: Methodssupporting

confidence: 66%

“…NMR spectra were identical to the reported data. 105 Compound 27 was isolated as a 10:1 mixture with methyl 3-(4-chlorophenyl)acrylate. See the 1 H NMR in the Supporting Information.…”

Section: S Y N T H E S I S O F ( E ) -M E T H Y L 4 -( N -( 2 -I O D ...mentioning

confidence: 99%

Ti/Ni-Mediated Inter- and Intramolecular Conjugate Addition of Aryl and Alkenyl Halides and Triflates

et al. 2014

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“…Interestingly, due to the weak C−Sn bond (278 kJ/mol in Me 4 Sn), 38 the addition to alkenes (vinylidene chloride, St, acrylonitrile, MMA, and dienes 125 ) is somewhat reversible 3 8 , 1 2 6 but that to alkynes is not. 38,68,69,127−129 As R 3 Sn • is nucleophilic, 38,88 131 or vinyl ketones, while under UV, Me 3 SnH adds to perfluorovinyls (CF 2 CF−Z, Z = Si, Ge, Sn, Re(CO) 5 ) 130,132,133 and norbornadiene. 134 Similarly, other Sn and Pb derivatives add to tetracyanoquinodimethane, quinones, 135−138 and reversibly to allenes, 139 dienes, 140,141 CF 2 CF(CF 3 ), and CF 2 CF 2 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…As R 3 Sn • is nucleophilic, , electron-poor alkenes are preferred, and Me 3 Sn • and Bu 3 Sn • from the UV irradiation of Me 6 Sn 2 or Bu 3 SnH add to fluoroalkenes, including VDF. Likewise, Bu 3 SnH adds radically to unpolymerizable, beta -substituted acrylates (R–CHCH(COOR′)) or vinyl ketones, while under UV, Me 3 SnH adds to perfluorovinyls (CF 2 CF–Z, Z = Si, Ge, Sn, Re(CO) 5 ) ,, and norbornadiene . Similarly, other Sn and Pb derivatives add to tetracyanoquinodimethane, quinones, − and reversibly to allenes, dienes, , CF 2 CF(CF 3 ), and CF 2 CF 2 .…”

Section: Resultsmentioning

confidence: 99%

“…It is thus conceivable that group 14 R 3 Q • (Q = C, Si, Ge, Sn, Pb) radicals could initiate an FRP by direct monomer addition, ,− hydride or halide abstraction from a suitable substrate, ,− reaction with O 2 , , etc., while a reversible P n –QR 3 bond would mediate a CRP. However, while some R 6 Q 2 or R 4 Q (Q = Si, Ge, Sn) systems were evaluated as UV co-initiators for acrylates, ,− R 3 Q-TEMPO adducts were suggested as CRP mediators, and Ph 3 C–CPh 3 poorly mediates styrene CRP, − the R 6 Sn 2 polymer photochemistry remains largely ignored, with no reports on initiations by R 3 Q • or R 3 Q • with R′X/R′H, on CRPs mediated by reversible termination with R 3 Q • , or on tin derivatives in FRP or CRP under visible light.…”

Section: Resultsmentioning

confidence: 99%

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Universal Group 14 Free Radical Photoinitiators for Vinylidene Fluoride, Styrene, Methyl Methacrylate, Vinyl Acetate, and Butadiene

et al. 2019

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Group 14 (Mt = Sn, Ge, Pb) R3MtX, R4Mt, and R6Mt2 complexes (R = alkyl, aryl; X = H, halide, etc.) are introduced as novel, universal, visible and black light bulb (BLB)/UV photoinitiators for free radical photopolymerization of alkenes, including vinylidene fluoride (VDF), vinyl acetate, methyl methacrylate, styrene, and butadiene. A comprehensive solvent, ligand and metal comparison for VDF indicates progressively faster BLB photopolymerizations in acetonitrile (ACN) ∼ dimethylacetamide (DMAc) < dimethyl sulfoxide (DMSO) < butanone < propylene carbonate < acetic anhydride ∼ cyclohexanone < dimethyl carbonate and especially in the photosensitizing acetone, where Me2SnI2 ∼ Ph3SnI ∼ Bu3Sn–N3 ∼ Bu3Sn–CH2–CHCH2 ≪ Bu3Sn–S–SnBu3 < Ph4Ge < Ph6Pb2 < Bu3Sn–I < Bu4Sn < Ph6Sn2 < Bu3Sn–Br < Ph6Ge2 < Oct4Sn < Bu4Ge < Bu3Sn–Cl < Ph4Pb < Bu3Sn–H ≪ Bu6Sn2 ≪ Me6Sn2 and where M n is controlled by solvent chain transfer. Photoinitiation results from a combination of R3Mt·, R·, and solvent (S·, e.g., CH3–CO–CH2·) radicals, where R6Sn2 (R = Me, Ph) initiates as R3Sn·, all Bu derivatives, as both Bu3Sn· and Bu·, and Ph4Mt and Ph6Mt2 (Ge, Pb), only indirectly via S·. Interestingly, while R3Sn–CH2–CF2-poly(vinylidene fluoride) (PVDF) eliminates R3SnF to afford CH2CF–PVDF macromonomers, nonfluorinated alkenes are initiated even in bulk under visible light and do not undergo R3SnH elimination.

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Preparation of Alkyls, Methylenes, and Aryls

Smith

2009

Compendium of Organic Synthetic Methods

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Conjugate Hydrostannation of Unsaturated Esters by Iodotin Hydride Ate Complex

Cited by 19 publications

References 10 publications

Ti/Ni-Mediated Inter- and Intramolecular Conjugate Addition of Aryl and Alkenyl Halides and Triflates

Ti/Ni-Mediated Inter- and Intramolecular Conjugate Addition of Aryl and Alkenyl Halides and Triflates

Universal Group 14 Free Radical Photoinitiators for Vinylidene Fluoride, Styrene, Methyl Methacrylate, Vinyl Acetate, and Butadiene

Preparation of Alkyls, Methylenes, and Aryls

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