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DOI: 10.1055/s-0031-1289539
Enantioselective Access to 3-Methylene-1H-indanol through Asymmetric Domino Allylstannylation-Heck Reaction
Publication History
Publication Date:
19 October 2011 (online)
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Abstract
By screening various chiral P,P-ligands in the palladium-catalyzed reaction of ortho-iodobenzaldehyde with allyl tributylstannane, a suitable ligand (Taniaphos) was identified that affords 3-methylene-1-indanol with an enantioselectivity of 96% ee. This result indicates that a ligated palladium intermediate is involved in the chirogenic step of the catalytic cycle (intramolecular electrophilic activation of the aldehyde function by ortho-palladation).
Key words
palladium - enantioselective catalysis - allyl-stannanes - intramolecular - Heck reaction - domino reactions - chiral P,P-ligands
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References and Notes
All minima of 9 were optimized with DFT, B3LYP/6-31G(d) using Gaussian 03.²¹
23TZVP is a triple-ζ basis set with polarization functions
25Typical procedure: 2-Iodobenzaldehyde
(4a; 116 mg, 0.5 mmol), [Pd2dba3] (10.4 mg,
10 µmol, 2 mol%) and ligand L15 (Taniaphos, 15 µmol,
3 mol%) were dissolved in anhydrous DMF (5 mL)
under an argon atmosphere. Allyl tributylstannane (0.31 mL, 1.0 mmol,
2 equiv) was added and the resulting mixture was stirred at 80 ˚C
for 15 h. After cooling to r.t. sat. aq KF (15 mL) was added and
the mixture was extracted with methyl tert-butyl
ether (3 × 20 mL). The combined organic
layers were washed with brine (20 mL), dried over MgSO4 and
solvents were evaporated. The residue was purified by flash chromatography
(SiO2-KF, 9:1; eluting with cyclohexane-EtOAc,
4:1) to give 9 (38 mg, 52%) as
a white-yellowish solid. The enantiomeric purity was determined
as 96% ee by means of chiral HPLC (Machery-Nagel Nucleocel
Delta S; n-hex-i-PrOH,
99:1; 0.5 mL/min); R
f
= 0.38
(Cyhex-EtOAc, 3:1); mp 71-72 ˚C; [α]D
²0 -9.1
(c 1.03, CDCl3); ¹H NMR:
(300 MHz, CDCl3):
δ = 2.42
(d, ³
J = 7
Hz, 1 H, OH), 2.61 (tdd, 4
J = 2.5
Hz, ³
J = 4 Hz, ²
J = 17 Hz,
1 H, H2A), 3.14 (tdd, 4
J = 2 Hz, ³
J = 7 Hz, ²
J = 17 Hz,
1 H, H2B), 5.07 (t, 4
J = 2 Hz,
1 H, H8A), 5.20 (dt, ³
J = 7 Hz, ³
J = 4 Hz,
1 H, H1), 5.50 (t, 4
J = 2.5
Hz, 1 H, H8B), 7.26-7.34, 7.39-7.45,
7.46-7.53 (3 × m, 4 × 1 H,
H4, H5, H6, H7); ¹³C NMR (75
MHz, CDCl3): δ = 42.4 (t, C2), 73.2
(d, C1), 104.2 (t, C8), 120.5, 125.0, 128.6, 128.7 (4 × d, C4,
C5, C6, C7), 140.1 (s, C3), 146.3, 146.9 (2 × s,
C3a, C7a); IR (ATR): 3305 (br, m), 3233 (br,
m), 3060 (w), 2921 (w), 2733 (w), 1641 (m), 1471 (m), 1423 (m),
1333 (s), 1044 (s), 873 (s), 756 (s), 730 (s) cm-¹;
GC-MS (Optima 1 MS, 10 psi, 50→300 ˚C): t
R = 6.51 min; MS
(EI, 70 eV): m/z (%) = 146
(42)[M]+, 145 (26), 131 (52),
128 (52), 117 (24), 103 (13), 91 (12), 77 (18), 63 (26), 39 (100);
HRMS: m/z calcd for
C10H10O: 146.073; found: 146.073 (±0.002).