Studies in group IV organometallic chemistry

Leusink, A.J.; Budding, H.A.; Marsman, J.W.

doi:10.1016/s0022-328x(00)83730-4

Cited by 145 publications

(48 citation statements)

References 5 publications

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“…As expected (19), introduction of an a methyl group results in a further shift to longer wavelengths (Entries 2,4). Similar trends are seen with P-tri-n-butylstannyl enones, although the bathochromic shifts (16)(17)(18)(19)Entries 6,8,10) associated with the n-Bu3Sn group are consistently larger than those related to the Me3Sn group. Finally, it is interesting to note that the molar absorptivities of the P-trirnethylstannyl enones are consistently greater than those of the tri-n-butylstannyl analogs.…”

Section: Introductionsupporting

confidence: 63%

(Trialkylstannyl)copper(I) reagents: preparation and reaction with α,β-unsaturated carbonyl systems. Preparation of β-trialkylstannyl α,β-unsaturated ketones

Piers¹,

Morton²,

Chong³

1987

Can. J. Chem.

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Reaction of Me3SnLi with 1 equivalent of CuBr•Me2S, PhSCu, Me2(MeO)C—C≡C—Cu, or CuCN in tetrahydrofuran (THF) affords the (trimethylstannyl)copper(I) reagents Me3SnCu•Me2S (1) and [Me3SnCuY]Li (Y = PhS (2), Me2(MeO)C—C≡C (4), CN (5)), respectively. Similarly, treatment of a THF solution of Me3SnLi with 0.5 equivalent of CuBr•Me2S provides (Me3Sn)2CuLi (3), while reaction of n-Bu3SnLi with PhSCu (1 equivalent) gives [n-Bu3SnCuSPh]Li (6). Reagents 2 and 6 readily transfer (in a conjugate sense) the R3Sn group to conjugated enones (e.g. 7–9) and structurally simple enoates (e.g. 10), but do not react with β,β-disubstituted α,β-unsaturated esters (e.g. 11–13). Reaction of reagent 2 with the enone 26 under "normal" conditions produces, in addition to the expected ketone 28, a significant amount of the double conjugate addition product 30. A similar result is obtained with ethyl propenoate (27). However, reaction of 26 and 27 with reagent 2 in the presence of acetic acid provides cleanly and efficiently the "simple" conjugate addition products 28 and 29, respectively. Reagent 1 does not react, or reacts very sluggishly, with α,β-unsaturated carbonyl compounds. β-Trialkylstannyl α,β-unsaturated ketones (e.g. 37–46) can be produced smoothly and efficiently by reaction of the corresponding β-iodo enones (e.g. 32–36) with reagents 2 (or 1) and 6.

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Section: Introductionsupporting

confidence: 63%

(Trialkylstannyl)copper(I) reagents: preparation and reaction with α,β-unsaturated carbonyl systems. Preparation of β-trialkylstannyl α,β-unsaturated ketones

Piers¹,

Morton²,

Chong³

1987

Can. J. Chem.

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“…The stereochemistry of the addition was readily apparent from the 1 H NMR spectra of compounds 4, which showed 3 J119 Sn,H = 56-64 Hz, fully in accord with an E geometry and overall cis addition of tin hydride. [25] The (3E)-configuration of compounds 4 could also be confirmed by the fact that values of 3 J13 C,…”

Section: Resultsmentioning

confidence: 79%

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

Zhao¹,

Yang²,

Xie³

et al. 2011

Eur J Org Chem

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Using palladium‐catalyzed addition reactions, a terminal alkyne, an acetylenic sulfone, and a tin hydride comprise the building blocks for the construction of difunctionalized 1,3‐dienes containing tin and sulfonyl groups in an atom‐economical fashion. Terminal alkynes 1 undergo clean cis addition to acetylenic sulfones 2 in the presence of catalytic amounts of palladium acetate and tri(2,6‐dimethoxyphenyl)phosphane to give (E)‐1‐sulfonyl‐substituted 1,3‐enynes 3 in excellent yields. Hydrostannylation of 1,3‐enynes 3 with tributyltin hydride in the presence of Pd(PPh3)4 affords regio‐ and stereoselectively (1E,3E)‐1‐sulfonyl‐3‐tributylstannyl‐substituted 1,3‐dienes 4 in excellent yields.

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“…Furthermore, in compounds such as 15 and 21, the magnitude of the coupling constants associated with the coupling of the alkene proton with the tin nuclei ("'Sn and "'Sn isotopes) is stereochemically diagnostic. It is known (9) Trimethylhydrazides are known to be very resistant to hydrolysis. It was, therefore, somewhat surprising to find that treatment of compound 20 with hot dilute hydrochloric acid for only 2 h totally converted this substrate into a single product (78% yield).…”

Section: Results and Discussion (A) General Considerationsmentioning

confidence: 99%

A total synthesis of (±)-triophamine

Piers¹,

Chong²,

Gustafson³

et al. 1984

Can. J. Chem.

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(1984). Treatment of ethyl 2-pentynoate (14) with lithium (phenylthio)(tri-11-butylstannyl)cuprate (12) afforded, in 76% yield, ethyl (2)-3-(tri-n-butylstanny1)-2-pentenoate (15). On the other hand, when compound 14 was allowed to react with the (tri-rzbutylstanny1)copper reagent 13, ethyl (E)-3-(tri-11-buty1stannyl)-2-pentenoate (21) was produced in 83% yield. Reduction (diisobutylaluminum hydride, ether) of the esters 15 and 21 gave the alcohols 1 6 and 22, respectively. Treatment of each of the latter substances with pyridine -sulfur trioxide complex, followed by further reduction of the resultant intermediates with lithium aluminum hydride, provided the geometrically isomeric alkenylstannanes 17 and 23. Conjugate addition of (E)-3-lithio-2-pentene (18) (formed by transmetalation of 17) to compound 19 produced the olefinic trimethylhydrazide 20, which was converted (diisobutylaluminum hydride, ether; pyridinium dichramate, dimethylformamide) into the corresponding carboxylic acid 2. Subjection of compound 23 to a sequence of reactions identical with that used for the conversion of 17 into 2 provided the isomeric acid 3, which was identical (infrared, 'H nmr) with the natural acid derived from triophamine (I). Conversion of 3 into the p-nitrophenyl ester 26, followed by condensation of the latter substance with guanidine, afforded a chromatographically separable mixture of (*)-triophamine (1) and the corresponding diastereomer.EDWARD PIERS, J. MICHAEL CHONG, KIRK GUSTAFSON et RAYMOND J. ANDERSEN. Can. J. Chem. 62, 1 (1984). Le pentyne-2 oate d'ethyl (14) riagit avec le (ph6nylthio)-(tri-n-butylstanny1)cuprate de lithium (12) pour donner, avec un rendement de 76%, le (2)-(tri-11-buty1stannyl)-3 pentkne-2 oate d'ithyle (15). Par ailleurs, quand on fait riagir le composi 14 avec le reactif (tri-n-butylstannyl)cuivre (13), on obtient avec un rendemcnt de 83%, le (E)-(tri-n-butylstanny1)-3 penthe-2 oate d'ithyle (21). Par reduction des esters 15 et 21 (par l'hydrure de diisobutylaluminium dans I'ither), on obtient respectivement les alcools 16 et 22. Ces alcools, par une riaction avec le complexe de pyridine -trioxyde de soufre suivie de la reduction des intermediaires resultants par I'alanate de lithium, conduisent aux alkinylstannates 17 et 2 3 qui sont des isomkres giometriques. L'addition conjuguke du (2)-lithio-3 penthe-2 (18) (forme par la transmetallation du composC 17) sur le composi 19 conduit au trimithylhydrazide olifinique 20 que I'on transforme (hydrure de diisobutylaluminium, ither; dichromate de pyridium, dimithylformamide) en I'acide carboxylique correspondant (2). Le compost? 23, soumis la suite dc riaction qui permet de transformer le compose 17 en composi 2, donne I'acide isomkre 3 que I'on a identifie (ir et rmn du 'H) i I'acide nature1 provenant de la triophamine (I). La transformation du composi 3 en esterp-nitrophknyle (26), suivie de la condensation de I'ester sur la guanidine, donne un milange de (*)-triophamine (1) et du diastCrioisomkre correspondant que I'on peut skparer par chromatogra...

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Studies in group IV organometallic chemistry

Cited by 145 publications

References 5 publications

(Trialkylstannyl)copper(I) reagents: preparation and reaction with α,β-unsaturated carbonyl systems. Preparation of β-trialkylstannyl α,β-unsaturated ketones

(Trialkylstannyl)copper(I) reagents: preparation and reaction with α,β-unsaturated carbonyl systems. Preparation of β-trialkylstannyl α,β-unsaturated ketones

Stereoselective Synthesis of Difunctionalized 1,3‐Dienes Containing Tin and Sulfonyl Groups by Palladium‐Catalyzed Regio‐ and Stereocontrolled Addition Reactions

A total synthesis of (±)-triophamine

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