References
<A NAME="RU25803ST-1A">1a</A>
Casiraghi G.
Zanardi F.
Battistini L.
Appendino G.
Chemtracts
1999,
12:
547
<A NAME="RU25803ST-1B">1b</A>
Saito S.
Yamamoto H.
Chem.-Eur. J.
1999,
5:
1959
<A NAME="RU25803ST-1C">1c</A>
Casiraghi G.
Zanardi F.
Battistini L.
Appendino G.
Rassu G.
Chem. Rev.
2000,
100:
1929
<A NAME="RU25803ST-2A">2a</A>
Paterson I.
Smith JD.
J. Org. Chem.
1992,
57:
3261
<A NAME="RU25803ST-2B">2b</A>
Cahard D.
Poirier J.-M.
Duhamel P.
Tetrahedron Lett.
1998,
39:
7093
<A NAME="RU25803ST-2C">2c</A> ATPH was used in the synthesis of Callipeltoside Aglycon, see:
Paterson I.
Davies RDM.
Marquez R.
Angew. Chem. Int. Ed.
2001,
40:
603
<A NAME="RU25803ST-2D">2d</A> The dienolates of g- or b-heteroatom-substituted a,b-unsaturated carbonyl compounds
are prone to vinylogous aldol reaction, see:
Krüger J.
Carreira EM.
J. Am. Chem. Soc.
1998,
120:
837
<A NAME="RU25803ST-2E">2e</A> See also:
Rassu G.
Pinna L.
Spanu P.
Zanardi F.
Battistini L.
Casiraghi G.
J. Org. Chem.
1997,
62:
4513
<A NAME="RU25803ST-2F">2f</A>
See also ref.1
<A NAME="RU25803ST-3A">3a</A>
Bluet G.
Campagne J.-M.
Tetrahedron Lett.
1999,
40:
5507
<A NAME="RU25803ST-3B">3b</A>
Bluet G.
Campagne J.-M.
J. Org. Chem.
2001,
66:
4293
<A NAME="RU25803ST-4A">4a</A>
Saito S.
Shiozawa M.
Nagahara T.
Nakadai M.
Yamamoto H.
J. Am. Chem. Soc.
2000,
122:
7847
<A NAME="RU25803ST-4B">4b</A>
Saito S.
Shiozawa M.
Yamamoto H.
Angew. Chem. Int. Ed.
1999,
38:
1769
<A NAME="RU25803ST-4C">4c</A>
Saito S.
Ito M.
Shiozawa M.
Yamamoto H.
J. Am. Chem. Soc.
1998,
120:
813
<A NAME="RU25803ST-4D">4d</A>
Saito S.
Yamazaki S.
Yamamoto H.
Angew. Chem. Int. Ed.
2001,
40:
3613
<A NAME="RU25803ST-4E">4e</A>
Saito S.
Sone T.
Murase M.
Yamamoto H.
J. Am. Chem. Soc.
2000,
122:
10216
<A NAME="RU25803ST-4F">4f</A> For detailed mechanistic aspects of the present vinylogous aldol reaction, see:
Saito S.
Nagahara H.
Shiozawa M.
Nakadai M.
Yamamoto H.
J. Am. Chem. Soc.
2003,
125:
6200
<A NAME="RU25803ST-4G">4g</A> For a review of ATPH, see:
Saito S.
Yamamoto H.
Chem. Commun.
1997,
1585
<A NAME="RU25803ST-5">5</A> Me-ATPH was prepared by the procedure similar to ATPH. The corresponding phenol
was prepared via four steps from commercial 2,6-dibromophenol. For experimental details,
see the forthcoming paper:
Ito H.
Nagahara T.
Ishihara K.
Saito S.
Yamamoto H.
Angew. Chem. Int. Ed.
2004, , in press
<A NAME="RU25803ST-6">6</A>
The use of a less amount of the ester, ATPH, and LTMP (1.0:2.2:1.2 equiv) proved less
productive. See also ref.4b
<A NAME="RU25803ST-7">7</A>
Typical Procedure: The reaction of menthyl crotonate (2a) with benzaldehyde (1a) is representative. To an anhydrous toluene (5.0 mL) solution of Me-ATPH (3.96 mmol)
were added 2a (179 mg, 0.80 mmol) and 1a (41 µL, 0.40 mmol) at -78 °C under argon. After the mixture was stirred for 20 min,
LTMP [generated by treatment of a solution of 2,2,6,6-tetramethylpiperidine (155 µL,
0.92 mmol) in THF (5.0 mL) with a 1.48 M hexane solution of n-BuLi (0.62 mL, 0.92 mmol) at 0 °C for 30 min] was transferred by a steel cannula
to the solution at -78 °C. The reaction mixture was stirred at this temperature for
1 h, quenched with aq NH4Cl, and the resulting suspension was extracted with Et2O. The organic layer was dried over Na2SO4 and concentrated. The residue was purified by column chromatography on silica gel
(Et2O-hexane, 1:2) to give aldol adduct 3a (88% yield, 60% de) as pale yellow solids. 2,6-Bis(4-methylphenyl)phenol was recovered
in more than 90% yield before the aldol product came off the column. Spectral and
analytical data of 3a: IR (neat): 3480, 3020, 2959, 2359, 1705, 1653, 1456 cm-1. 1H NMR (300 MHz, CDCl3): δ = 7.38-7,26 (m, 5 H), 6.95 (m, 1 H), 5.90 (dt, J = 1.5, 15.6 Hz, 1 H), 4.84 (m, 1 H), 4.73 (dt, J = 4.2, 10.8 Hz, 1 H), 2.64 (m, 2 H), 1.98 (m, 1 H), 1.92 (m, 1 H), 0.89 (dd, J = 4.5, 6.9 Hz, 6 H), 0.75 (d, J = 6.9 Hz, 3 H), 2.10-0.80 (m, 7 H). 13C NMR (75 MHz, CDCl3): δ = 166.0, 144.6, 143.6, 128.5, 127.8, 125.7, 124.2, 74.1, 73.0, 47.0, 41.9, 40.9,
34.2, 31.3, 26.2, 23.5, 22.0, 20.7, 16.4. Anal. Calcd for C21H30O3: C, 76.33; H, 9.15. Found: C, 76.12; H, 9.43. The de was determined by chiral HPLC
analysis after converting 3a into the corresponding diol {e.g., [α]D
25 = +20.9 (c = 1.13, CHCl3) for 73% ee}. Retention time data (column: OD-H; hexane-i-PrOH = 30:1 with a flow rate of 0.5 mL/min). (1S)-5-Hydroxy-1-phenyl-3-pentenol: t
R
= 84.2 min; (1R)-diol: t
R
= 90.7 min. The absolute configuration of 3a was determined by conversion to the known sample, 3-acetoxy-3-phenylpropionic acid,
as described in the literature procedure, see ref. 3b. γ-Adduct 5a was also derived to the above diol by reduction of the ester carbonyl and partial
reduction of the triple bond with AlH3.
<A NAME="RU25803ST-8">8</A>
Significant effects of second equivalent of ATPH, which presumably activates the aldehyde
partner, needs further investigation. In the absence of the second ATPH, considerable
decrease in chemical yields was consistently observed.
<A NAME="RU25803ST-9">9</A> C3-symmetry in chiral recognition, see:
Moberg C.
Angew. Chem. Int. Ed.
1998,
37:
248
<A NAME="RU25803ST-10">10</A>
Me-ATPH-2a complex: 1H NMR (300 MHz, toluene-d
8):
δ = 7.70-6.50 (m, 39 H), 5.99 (qd, J = 7.2, 25.4 Hz, 1 H), 4.76 (d, J = 25.6 Hz, 1 H), 3.66 (m, 1 H), 2.05 (s, 18 H), 1.68 (br s, 1 H), 1.36 (m, 2 H),
1.20 (br d, J = 11.7 Hz), 0.93 (d,
J = 6.9 Hz, 3 H), 0.78 (d, J = 6.9 Hz, 3 H), 0.64 (d, J = 6.9 Hz, 3 H), 0.60 (d, J = 6.0 Hz, 3 H), 1.15-0.56 (m, 4 H), 0.50 (br d, J = 11.7 Hz, 1 H). The Me-ATPH-2a complex is highly likely to adopt a most favorable diastereomeric conformation with
a negligible formation of other distinct diastereomers. See also ref.5 for the X-ray single crystal structure of a homochiral ester complex of ATPH.