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DOI: 10.1055/s-0029-1218297
Silver-Catalyzed Intermolecular Hydroamination of Alkenes and 1,3-Dienes
Publikationsverlauf
Publikationsdatum:
15. Oktober 2009 (online)
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Abstract
Silver triflate is used as efficient catalyst for the intermolecular addition of 4-toluenesulfonamide to alkenes under thermal or microwave heating. The hydroamination of 1,3-dienes can be performed at 85 ˚C with low catalyst loading (0.1-5 mol%) or at room temperature using 1 mol% of AgOTf, the use of HOTf affording similar results.
Key words
alkenes - conjugated dienes - hydroamination - sulfonamides - silver catalysts
- For reviews, see:
-
1a
Müller TE.Hultzsch KC.Yus M.Foubelo F.Tada M. Chem. Rev. 2008, 108: 3795 -
1b
Wolfe JP. Synlett 2008, 2913 -
1c
Shen HC. Tetrahedron 2008, 64: 3885 -
1d
Severin R.Doye S. Chem. Soc. Rev. 2007, 36: 1407 -
1e
Widenhoefer RA.Han X. Eur. J. Org. Chem. 2006, 4555 -
1f
Hazari N.Mountford P. Acc. Chem. Res. 2005, 38: 839 -
1g
Hultzsch KC. Adv. Synth. Catal. 2005, 437: 367 -
1h
Alonso F.Beletskaya IP.Yus M. Chem. Rev. 2004, 104: 3079 -
1i
Müller TE.Beller M. Chem. Rev. 1998, 98: 675 -
2a
Talluri SK.Sudalai A. Org. Lett. 2005, 7: 855 -
2b
Anderson LL.Arnold J.Bergman RG. J. Am. Chem. Soc. 2005, 127: 14542 -
2c
Li Z.Zhang J.Brouwer C.Yang C.-G.Reich NW.He C. Org. Lett. 2006, 8: 4175 -
2d
Rosenfeld DC.Shekhar S.Takemiya A.Utsunomiya M.Hartwig JF. Org. Lett. 2006, 8: 4179 -
2e
Motokura K.Nakagiri N.Mori K.Mizugaki T.Ebitani K.Jitsukawa K.Kaneda K. Org. Lett. 2006, 8: 4617 -
2f
Marcsekova I.Doye S. Synthesis 2007, 145 -
2g
Jazzar R.Dewhurst RD.Bourg JB.Donnadieu B.Canac Y.Bertrand G. Angew. Chem. Int. Ed. 2007, 46: 2899 -
2h
Yang L.Xu LW.Xia CG. Tetrahedron Lett. 2008, 49: 2882 -
2i
Li X.Ye S.He C.Yu Z.-X. Eur. J. Org. Chem. 2008, 4296 -
2j
Yadav JS.Reddy BVS.Raju A.Ravindar K.Narender R. Lett. Org. Chem. 2008, 5: 651 -
2k
Yang L.Xu L.-W.Xia C.-G. Synthesis 2009, 1969 -
3a
Cheng X.Xia Y.Wei H.Xu B.Zhang C.Li Y.Qian G.Zhang X.Li K.Li W. Eur. J. Org. Chem. 2008, 1929 -
3b
Yang L.Xu L.-W.Gao Y.-H.Sun W.Xia C.-G. Synlett 2009, 1167 ; and references cited therein -
4a
Zhang J.Yang C.-G.He C. J. Am. Chem. Soc. 2006, 128: 1798 -
4b
Brouwer C.He C. Angew. Chem. Int. Ed. 2006, 45: 1744 -
4c
Han X.Widenhoefer RA. Angew. Chem. Int. Ed. 2006, 45: 1747 -
4d
Nishina N.Yamamoto N. Angew. Chem. Int. Ed. 2006, 45: 3314 -
4e
Liu X.-Y.Li C.-H.Che C.-M. Org. Lett. 2006, 8: 2707 -
4f
Kovács G.Ujaque G.Lledós A. J. Am. Chem. Soc. 2008, 130: 853 -
4g
Giner X.Nájera C. Org. Lett. 2008, 10: 2919 -
4h
Zhang Z.Lee SD.Widenhoefer RA. J. Am. Chem. Soc. 2009, 131: 5372 - 5
Harrison TJ.Kozak JA.Corbella-Pané M.Dake GR. J. Org. Chem. 2006, 71: 4525 - 6
Gao H.Zhang J. Adv. Synth. Catal. 2009, 351: 85 - 7
Carney JM.Donoghue PJ.Wuest WM.Wiest O.Helquist P. Org. Lett. 2008, 10: 3903
References and Notes
General Procedure
for the Hydroamination of Alkenes and Dienes
To a
mixture of silver salt (see Tables
[¹]
and
[²]
) and sulfonamide (171
mg, 1 mmol) in dry solvent (2 mL, see Tables
[¹]
and
[²]
) was added the alkene
or 1,3-diene (4 mmol) with magnetic stirring in a sealed tube under
argon atmosphere in the dark. For neat experiments (see Table
[²]
, entries 6-8)
no solvent was added. After the corresponding reaction time under
the conditions indicated in Tables
[¹]
and
[²]
(for microwave heating
the vessel was sealed with a pressure lock, and the mixture was
heated at 90 ˚C in a CEM Discover MW reactor at 70 W, 0.69
bar with air stream cooling during 30 min), to the reaction mixture
cooled at r.t. was added H2O (2 mL) and brine (2 drops).
The organic layer was separated, and the aqueous phase was extracted
with EtOAc (2 × 10 mL). All organic phases
were mixed, dried with MgSO4, and evaporated. Pure products
were obtained by recrystallization or by flash chromatography.
Crystallographic data (excluding structure
factors) have been deposited with the Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk./data_request/cif
as supplementary publication no. CCDC 748465 [unit cell parameters: a 12.2371 (16), b 17.627
(2), c 7.9272 (11),
β 105.117 (3), space group P21/c].