Triorganotin Hydrides Research Articles

Organotin compounds: XI. Organotin hydride additions to various methyl dihydronaphthalenecar☐ylates

Free radical hydrostannation of methyl 3,4-dihydronaphthalene-1-car☐ylate (I), methyl 3,4-dihydronaphthalene-2-car☐ylate (III), and methyl 1,4-dihydronaphthalene-2-car☐ylate (V) with triorganotin hydrides, R 3SnH (R = Me, n-Bu, Ph) gives the energetically unfavourable cis products, 2-triorganostannyl-1,2,3,4-tetrahydronaphthalene-1-car☐ylate (II), 1-triorganostannyl-1,2,3,4-tetrahydronaphthalene-2-car☐ylate (IV), and 3-triorganostannyl-1,2,3,4-tetrahydronaphthalene-2-car☐ylate (VI) in high yields, via a trans addition of the tin hydrides. The hydride abstractions by the intermediate 2-, 1-, 3-triorganostannyl-1,2,3,4-tetrahydronapththyl radicals (XI, XII and XIII respectively) take place stereospecifically and exclusively from the less-hindered ring side. The structures of the isomers II, IV, and VI, were established by (a) their transformation into the corresponding chlorodiorganostannyl derivatives VIII, IX, and X, which were shown spectroscopically to have cis stereochemistries by intramolecular complexation of the ester group, and (b) their NMR data. Full 1H, 13C, and 119Sn NMR data are given.

ChemInform Abstract: Reduction of Thionoesters to Ethers by Triorganotin Hydrides.

Abstract Esters 1 are efficiently deoxygenated to the corresponding ethers 3 in two steps by first conversion to the thionoesters 2 and subsequent reduction of these by triorganotin hydrides.

ChemInform Abstract: Substituent Effects Upon the Kinetics of Hydrogen Transfer from Triorganotin Hydrides to the 5‐Hexen‐1‐yl Radical.

AbstractSteric and electronic effects are probed for the hydrogen atom transfer reaction of triorganotin hydrides such as (II) to the 5‐hexen‐1‐yl radical derived from (I).

Substituent effects upon the kinetics of hydrogen transfer from triorganotin hydrides to the 5-hexen-1-yl radical

Substituent effects upon the kinetics of hydrogen transfer from triorganotin hydrides to the 5-hexen-1-yl radical

REDUCTION OF THIONOESTERS TO ETHERS BY TRIORGANOTIN HYDRIDES

Abstract Esters 1 are efficiently deoxygenated to the corresponding ethers 3 in two steps by first conversion to the thionoesters 2 and subsequent reduction of these by triorganotin hydrides.

ChemInform Abstract: RHODIUM CATALYZED DEHYDROGENATION OF TRIORGANOTIN HYDRIDES AND MERCAPTANS, PREPARATION OF TRIORGANOTIN MERCAPTIDES

Chemischer InformationsdienstVolume 12, Issue 49 Organoelement Compounds ChemInform Abstract: RHODIUM CATALYZED DEHYDROGENATION OF TRIORGANOTIN HYDRIDES AND MERCAPTANS, PREPARATION OF TRIORGANOTIN MERCAPTIDES J. J. TALLEY, J. J. TALLEYSearch for more papers by this authorA. M. COLLEY, A. M. COLLEYSearch for more papers by this author J. J. TALLEY, J. J. TALLEYSearch for more papers by this authorA. M. COLLEY, A. M. COLLEYSearch for more papers by this author First published: December 8, 1981 https://doi.org/10.1002/chin.198149283Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume12, Issue49December 8, 1981 RelatedInformation

Rhodium catalyzed dehydrogenation of triorganotin hydrides and mercaptans, preparation of triorganotin mercaptides

Triorganotin hydrides react with a variety of aliphatic and aromatic mercaptans in the presence of a catalytic amount of chlorotris(triphenolphosphine)rhodium to produce triorganotin mercaptides.

Stereoselective substitution reactions at the metal atom of optically active organo-tin compounds

Abstract

Organomentallic compounds : LXIII. Synthesis, optical stability, stereo-selective and -specific reactions of chiral triorganotin hydrides

Optically active triorganotin hydrides have been synthesized by asymmetric reduction of the corresponding halides. These optically stable compounds undergo stereoselective conversions into other optically stable compounds such as tetraorganotin compounds (by reaction with diazomethane or with bifluorenylidene) or hexaorganoditin compounds (by reaction in the presence of palladium) or into optically unstable compounds such as methylneophylphenyltin chloride (by reaction with CCl 4). The HD exchange between optically active methylneophylphenyltin hydride (deuteride) and triphenyltin deuteride (hydride) occurs with retention of configuration at the metal atom.

ChemInform Abstract: SYNTHESIS AND OPTICAL STABILITY OF CHIRAL TRIORGANOTIN HYDRIDES

Chemischer InformationsdienstVolume 8, Issue 27 Organoelement Compounds ChemInform Abstract: SYNTHESIS AND OPTICAL STABILITY OF CHIRAL TRIORGANOTIN HYDRIDES M. GIELEN, M. GIELENSearch for more papers by this authorY. TONDEUR, Y. TONDEURSearch for more papers by this author M. GIELEN, M. GIELENSearch for more papers by this authorY. TONDEUR, Y. TONDEURSearch for more papers by this author First published: July 5, 1977 https://doi.org/10.1002/chin.197727276Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat No abstract is available for this article. Volume8, Issue27July 5, 1977 RelatedInformation

Synthesis and optical stability of chiral triorganotin hydrides

The first optically-active triorganotin hydrides are reported viz.: (+)−and ()-methylneophylphenyltin hydride and ()-t-butylneophylphenyltin hydride; they are fairly optically stable.

Chiral Organotin Compounds

AbstractSeveral classes of organotin compounds are configurationally stable within the NMR time‐scale and are even optically stable for weeks. Optically active tetraorganotin compounds, triorganotin hydrides and an optically active (triorganogermyl)triorganotin compound have been synthesized. Two reactions transforming optically active triorganotin hydrides into optically active tetraorganotin compounds are described.

Configurational Stability of Triorganostannylamines, ‐Phosphines and ‐Arsines

AbstractStannylamines, ‐phosphines and ‐arsines are shown to be configurationally stable within the NMR time‐scale, even in the presence of a strong nucleophile. The configurational stability of triorganotin hydrides and the configurational unstability of triorganotin halide has been checked.

Hydrostannation of 2-vinyl-4,4,6-trimethyl-1,3,2-dioxaborinane

The hydrostannation of 2-vinyl-4,4,6-trimethyl-1,3,2-dioxaborinane (VTDB) with trimethyl-, triethyl-, tripropyl-, tributyl-, and triphenyltin hydrides has been studied. The hydrostannation reactions, in all the cases studied, provided adducts with the organotin moiety at the β-carbon position; there was no indication of adducts with the organotin moiety at the α-carbon position. The reaction rate of tributyltin hydride with VTDB was accelerated by azobis(isobutyronitrile) (AIBN), retarded by galvinoxyl radical, and unaffected by change in solvent polarity. These observations confirm a free radical process for the hydrostannation of VTDB with triorganotin hydrides.

Binuclear organometallic compounds. Part II. Reactions of triorganotin hydrides with iridium(I) and rhodium(I) complexes

Hydrostannation of the iridium(I) complexes, trans-IrXCOL2(where X = Cl, Br, or I; L = PPh3, PPh2Me, or PPhEt2) by the tri-organotin hydrides, R3SnH (where R = Me, Et, or Ph), yields the iridium(III) species, R3SnIr-HXCOL2, the stereochemical configurations of which are discussed on the basis of i.r. and n.m.r. data. The rhodium(I) complex, RhClCO(PPhEt2)2 does not react with tri-organotin hydrides, and, although RhCl(PPh3)3 does react, hydrostannation does not occur.

Chemistry of the metal carbonyls. Part LI. Organotin–(carbonyl)ruthenium complexes

Treatment of the pale yellow solid obtained from dodecacarbonyltriruthenium and sodium in liquid ammonia with triorganotin chlorides affords tin–ruthenium bonded complexes (R3Sn)2Ru(CO)4. These complexes can also be prepared by treating triorganotin hydrides with dodecacarbonyltriruthenium, when additional products of molecular formula R10Sn4Ru2(CO)6 are produced. Both (Me3Sn)2Ru(CO)4 and Me10Sn4Ru2(CO)6 are formed in low yields by heating dimethylstannane or hexamethylditin with dodecacarbonyltriruthenium. The course of these reactions is somewhat different from those observed previously with iron carbonyls. Further differences in the two systems are revealed by the existence of cis- and trans-isomers of (R3Sn)2Ru(CO)4, compared with the uniform cis-symmetry of the known iron analogues. The i.r. spectra of the new compounds in the carbonyl stretching region are reported, and some aspects of their mass spectra discussed.

Addition of organotin hydrides across the nitrogen‐nitrogen double bond; Hydrogenolysis of the tin‐nitrogen bond by organotin hydrides

AbstractTriorganotin hydrides readily add across the nitrogen‐nitrogen double bond of azobenzene and diethyl azodicarboxylate to produce organotin‐substituted hydrazine derivatives.The reduction of these azo compounds and of aryl isocyanates by triorganotin hydrides proceeds by formation of a 1: 1 adduct and subsequent hydrogenolysis of the tin‐nitrogen bond of the adduct.