Abstract
Atom-efficient organoactinide-catalyzed intermolecular hydrothiolation of terminal alkynes is achieved by Th(IV) and U(IV) complexes to yield vinyl sulfides. The conversion is highly Markovnikov selective and is capable of utilizing aromatic, benzylic, and aliphatic thiols. Kinetic measurements of the transformation mediated by Me2SiCp2'Th[CH 2(TMS)]2 (1a; Cp' =n5-Me4C 5) shows the reaction is zero-order in [thiol], first-order in [1a], first-order in [alkyne] at lower alkyne concentrations, and zero-order at higher [alkyne]. The proposed catalytic cycle invokes turnover-limiting insertion of the alkyne into the Th-S bond followed by a rapid Th-C bond protonolysis. All reactions except entries 7 and 8 are quantitative by 1H NMR.
| Original language | English |
|---|---|
| Pages (from-to) | 2062-2063 |
| Number of pages | 2 |
| Journal | Journal of the American Chemical Society |
| Volume | 131 |
| Issue number | 6 |
| DOIs | |
| Publication status | Published - Feb 18 2009 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Organoactinide-mediated hydrothiolation of terminal alkynes with aliphatic, aromatic, and benzylic thiols. / Weiss, Charles J.; Wobser, Stephen D.; Marks, Tobin J.
In: Journal of the American Chemical Society, Vol. 131, No. 6, 18.02.2009, p. 2062-2063.Research output: Contribution to journal › Article
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TY - JOUR
T1 - Organoactinide-mediated hydrothiolation of terminal alkynes with aliphatic, aromatic, and benzylic thiols
AU - Weiss, Charles J.
AU - Wobser, Stephen D.
AU - Marks, Tobin J
PY - 2009/2/18
Y1 - 2009/2/18
N2 - Atom-efficient organoactinide-catalyzed intermolecular hydrothiolation of terminal alkynes is achieved by Th(IV) and U(IV) complexes to yield vinyl sulfides. The conversion is highly Markovnikov selective and is capable of utilizing aromatic, benzylic, and aliphatic thiols. Kinetic measurements of the transformation mediated by Me2SiCp2'Th[CH 2(TMS)]2 (1a; Cp' =n5-Me4C 5) shows the reaction is zero-order in [thiol], first-order in [1a], first-order in [alkyne] at lower alkyne concentrations, and zero-order at higher [alkyne]. The proposed catalytic cycle invokes turnover-limiting insertion of the alkyne into the Th-S bond followed by a rapid Th-C bond protonolysis. All reactions except entries 7 and 8 are quantitative by 1H NMR.
AB - Atom-efficient organoactinide-catalyzed intermolecular hydrothiolation of terminal alkynes is achieved by Th(IV) and U(IV) complexes to yield vinyl sulfides. The conversion is highly Markovnikov selective and is capable of utilizing aromatic, benzylic, and aliphatic thiols. Kinetic measurements of the transformation mediated by Me2SiCp2'Th[CH 2(TMS)]2 (1a; Cp' =n5-Me4C 5) shows the reaction is zero-order in [thiol], first-order in [1a], first-order in [alkyne] at lower alkyne concentrations, and zero-order at higher [alkyne]. The proposed catalytic cycle invokes turnover-limiting insertion of the alkyne into the Th-S bond followed by a rapid Th-C bond protonolysis. All reactions except entries 7 and 8 are quantitative by 1H NMR.
UR - http://www.scopus.com/inward/record.url?scp=67849114613&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=67849114613&partnerID=8YFLogxK
U2 - 10.1021/ja808764q
DO - 10.1021/ja808764q
M3 - Article
C2 - 19170549
AN - SCOPUS:67849114613
VL - 131
SP - 2062
EP - 2063
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 6
ER -