syn-Selective Rhodium(I)-Catalyzed Allylations of Ketimines Proceeding through a Directed CH Activation/Allene Addition Sequence†
Duc N. Tran
Laboratory of Organic Chemistry, ETH Zurich, Wolfgang-Pauli-Strasse 10, HCI H 304, 8093 Zurich (Switzerland), Fax: (+41) 44-632-1328 http://www.cramer.ethz.ch
Search for more papers by this authorDr. Nicolai Cramer
Laboratory of Organic Chemistry, ETH Zurich, Wolfgang-Pauli-Strasse 10, HCI H 304, 8093 Zurich (Switzerland), Fax: (+41) 44-632-1328 http://www.cramer.ethz.ch
Search for more papers by this authorDuc N. Tran
Laboratory of Organic Chemistry, ETH Zurich, Wolfgang-Pauli-Strasse 10, HCI H 304, 8093 Zurich (Switzerland), Fax: (+41) 44-632-1328 http://www.cramer.ethz.ch
Search for more papers by this authorDr. Nicolai Cramer
Laboratory of Organic Chemistry, ETH Zurich, Wolfgang-Pauli-Strasse 10, HCI H 304, 8093 Zurich (Switzerland), Fax: (+41) 44-632-1328 http://www.cramer.ethz.ch
Search for more papers by this authorWe thank Dr. B. Schweizer for X-ray crystallographic analysis of compound 6 ce and the ETH Zurich (ETH-16 08-3) for funding. We are grateful to Solvias AG for MeOBiphep ligands, Takasago International Corporation for Segphos, and Umicore AG & Co. KG for rhodium salts. N.C. thanks the Fonds der Chemischen Industrie for a Liebig Fellowship.
Graphical Abstract
On a Rh-oll: Rhodium(I)-catalyzed CH activations of ketimines and subsequent carborhodation of an allene led to an allyl metal species, which then allylated the imine directing group to give highly functionalized methylene dihydroindenyl amines (see scheme) with excellent regio- and diastereoselectivity.
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- 12Unsubstituted ketimines are readily available by the addition of lithium or Grignard reagents to nitriles or from the ketones by a treatment with ammonia and titanium tetrachloride. The purity of the imines 1 is of great importance for the conversion of the reaction. Substituted diaryl ketimines (NBn, NTs, NAc, NCO2Me) give the corresponding product 6 only very low yields.
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- 15The carbonyl stretching frequency of the corresponding [LRh(Cl)CO] complex is a convenient indicator for the relative π acidity of the phosphines ligands: L1: ν=2004 cm−1, L2: ν=2017 cm−1, L4: ν=1984 cm−1, L5: ν=2000 cm−1, binap: ν=2006 cm−1 (data obtained on a Varian 640-IR FT-IR spectrometer).
- 16The allMeOBiphep ligand (L5) was developed at F. Hoffmann-La Roche AG: EP0926151A1. However, its performance in catalytic reactions has never been disclosed. rac-L5 is conveniently prepared in two steps from tris-3,4,5-trimethoxyphosphineoxide in 59 % yield.
- 17The obtained e.r. values for 6 aa were: 57:43 ((R)-binap), 60:40 (L1), 71:29 (L3).
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- 19Crystallographic data for 6 ce: C18H13F2NO, M=297.30, monoclinic, space group C2/c, a=25.9672(6) Å, b=7.3668(2) Å, c=17.6121(5) Å, β=124.3779(13)°, V=2780.63(13) Å3, Z=8, Dcalc=1.420 Mg m−3, T=123 K, reflections collected: 5596, independent reflections: 3183 (Rint=0.046), R(all)=0.0660, wR(gt)=0.1334. CCDC 779690 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
- 20The absolute configuration of (−)-6 ge has not yet been determined.
