Asymmetric Cyanosilylation of Aldehydes Catalyzed by Novel Chiral Tetraaza-Titanium Complexes

Yanling Liu; Xiaohua Liu; Junguo Xin; Xiaoming Feng

doi:10.1055/s-2006-939724

LETTER

Asymmetric Cyanosilylation of Aldehydes Catalyzed by Novel Chiral Tetraaza-Titanium Complexes

Yanling Liu^a, Xiaohua Liu^a, Junguo Xin^a, Xiaoming Feng*^a,b
^a Key Laboratory of Green Chemistry & Technology (Sichuan University), Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China
Fax: +86(28)85418249; e-Mail: xmfeng@scu.edu.cn;
^b State Key Laboratory of Biotherapy, West China Hospital, Sichuan University, Chengdu 610041, China

Abstract

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Abstract

The asymmetric addition of trimethylsilyl cyanide (TMSCN) to a range of aldehydes was efficiently catalyzed by a novel, easily prepared C ₂-symmetric chiral tetraaza-Ti(IV) complex in high yields with up to 92% ee under mild conditions. A negative nonlinear effect between the ee of the ligand and the ee of the product was observed.

Key words

C ₂-symmetric chiral tetraaza ligand - cyanosilylation - aldehydes - enantioselectivity - organotitanium

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Referenzen

References and Notes

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General Procedure for the Preparation of C ₂ -Symmetric Tetraaza Ligands.
Step 1: To a solution of S-2-tert-butoxycarbonyl-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (3.467 g, 12.5 mmol) in CH₂Cl₂ was added Et₃N (2.1 mL, 15 mmol) and isobutyl isobutyl chlorocarbonate (1.8 mL, 13.75 mmol) at 0 °C under stirring. After 20 min, (1R,2R)-1,2-diphenyl-ethane-1,2-diamine (1.061 g, 5 mmol) was added. It was warmed to r.t. and stirred for 10 h. The mixture was washed with 1 M KHSO₄, sat. NaHCO₃ and brine, dried over anhyd MgSO₄ and concentrated. The residue was used for the next step directly.
Step 2: To a solution of the residue in CH₂Cl₂ (20 mL) was added TFA (12.5 mL) and stirred for 5 h. Then the solution was concentrated in vacuo, and H₂O (25 mL) was added. The pH of the mixture was brought into the range of 11-12 by the addition of 2 M NaOH. The aqueous phase was extracted with CH₂Cl₂. The CH₂Cl₂ extracts were pooled, washed with brine, dried over anhyd MgSO₄ and evaporated in vacuo. The crude product was purified by recrystallization to afford C ₂-symmetric tetraaza ligands 2d as a white solid (2.388 g, 90% yield).

The following are the physical, NMR and HRMS data of 2d: mp 200.0-201.1 °C; [α]_D ²⁵ -86.3 (c 1.62, CH₂Cl₂). ¹H NMR (400 MHz, CDCl₃): δ = 8.09 (2 H, s), 6.95-7.26 (18 H, m), 5.31 (2 H, m), 3.88 (2 H, m), 3.48 (4 H, m), 2.74-3.07 (4 H, m), 2.3 (2 H, m) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 30.5, 47.1, 56.3, 58.8, 125.6, 126.2, 126.4, 127.6, 127.7, 128.5, 129.2, 133.7, 135.4, 138.7, 173.2 ppm. HRMS (ESI): m/z calcd for C₃₄H₃₄N₄O₂ 531.2755 [M + H]⁺; found: 531.2760 [M + H]⁺.

General Procedure for Asymmetric Cyanosilylation of Aldehydes. To a solution of 2d (19.9 mg, 0.0375 mmol) and p-nitro-benzoic acid (3.1 mg, 0.0186 mmol) in CH₂Cl₂ (0.4 mL) was added Ti(Oi-Pr)₄ (1 M in toluene, 75 µL, 0.075 mmol) and CH₂Cl₂ (0.5 mL) at r.t., then the mixture was stirred at 35 °C for 1 h under N₂ atmosphere. To this solution, aldehyde (0.25 mmol), TMSCN (70 µL, 0.525 mmol) and CH₂Cl₂ (0.1 mL) were added, in that order, at 0 °C under an N₂ atmosphere. After the aldehyde was completely converted (monitored by TLC, 14-36 h), the crude product was purified by column chromatography to give the corresponding cyanohydrin trimethylsilyl ether as colorless oil. After conversion into the acetate, the ee value was determined.

Physical, NMR and HRMS data of 1a: mp 140.5-141.3 °C; [α]_D ²⁵ -73.3° (c 1.86, CH₂Cl₂). ¹H NMR (600 MHz, CDCl₃): δ = 8.37 (s, 2 H), 7.06-7.12 (m, 6 H), 7.00-7.02 (m, 4 H), 5.14 (m, 2 H), 3.63 (m, 2 H), 2.93 (m, 2 H), 2.86 (m, 2 H), 2.23 (s, 2 H), 2.07 (m, 2 H), 1.76 (m, 2 H), 1.63 (m, 4 H) ppm. ¹³C NMR (100 MHz, CDCl₃): δ = 26.0, 30.6, 47.2, 58.1, 60.5, 127.4, 127.5, 128.2, 139.0, 174.5 ppm. HRMS (ESI): m/z calcd for C₂₄H₃₀N₄O₂: 407.2442 [M + H]⁺; found: 407.2456 [M + H]⁺.

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Only 16-24% ee was obtained for aliphatic aldehydes.