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Synlett
Volumn , Issue 3, 2008, Pages 394-398
The development of an asymmetric Nicholas reaction using chiral phosphoramidite ligands
Author keywords

Asymmetric synthesis; Ligands; Nucleophiles; Organometallic reagents; Phosphorus
Indexed keywords

ALCOHOL DERIVATIVE; CARBON; CARBONYL DERIVATIVE; COBALT; ETHER; LEWIS ACID; LIGAND; PHOSPHORAMIDOUS ACID DERIVATIVE;
EID: 39749115558     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-2008-1032059     Document Type: Article
Times cited : (12)
References (61)
  • 1
    • 33845281351 scopus 로고
    • For reviews on the Nicholas reaction, see: a
    • For reviews on the Nicholas reaction, see: (a) Nicholas, K. M. Acc. Chem. Res. 1987, 20, 207.
    • (1987) Acc. Chem. Res , vol.20 , pp. 207
    • Nicholas, K.M.1
  • 42
    • 39749145465 scopus 로고    scopus 로고
    • For ligand 2a, see ref. 19a.
    • (a) For ligand 2a, see ref. 19a.
  • 43
    • 2942599460 scopus 로고    scopus 로고
    • For ligand 2d, see: Lefort, L.; Boogers, J. A. F.; de Vries, A. H. M.; de Vries, J. G. Org. Lett. 2004, 6, 1733.
    • (b) For ligand 2d, see: Lefort, L.; Boogers, J. A. F.; de Vries, A. H. M.; de Vries, J. G. Org. Lett. 2004, 6, 1733.
  • 44
    • 33644659716 scopus 로고    scopus 로고
    • For ligand 2e, see: Panella, L.; Aleixandre, A. M.; Kruidhof, G. J.; Robertus, J.; Feringa, B. L.; de Vries, J. G.; Minnaard, A. J. J. Org. Chem. 2006, 71, 2026.
    • (c) For ligand 2e, see: Panella, L.; Aleixandre, A. M.; Kruidhof, G. J.; Robertus, J.; Feringa, B. L.; de Vries, J. G.; Minnaard, A. J. J. Org. Chem. 2006, 71, 2026.
  • 45
    • 0038251459 scopus 로고    scopus 로고
    • For ligand 2f, see: Boiteau, J.-G.; Imbos, R.; Minnaard, A. J.; Feringa, B. L. Org. Lett. 2003, 5, 681.
    • (d) For ligand 2f, see: Boiteau, J.-G.; Imbos, R.; Minnaard, A. J.; Feringa, B. L. Org. Lett. 2003, 5, 681.
  • 46
    • 39749183845 scopus 로고    scopus 로고
    • For ligand 2g, see ref. 19b.
    • (e) For ligand 2g, see ref. 19b.
  • 47
    • 39749156151 scopus 로고    scopus 로고
    • For ligands 2h and 2i, see ref. 21.
    • (f) For ligands 2h and 2i, see ref. 21.
  • 48
    • 39749115295 scopus 로고    scopus 로고
    • For ligands 2j and 2k, see ref. 16a.
    • (g) For ligands 2j and 2k, see ref. 16a.
  • 49
    • 0012824998 scopus 로고    scopus 로고
    • For ligands 21 and 2m, see: Peña, D.; Minnaard, A. J.; de Vries, A. H. M.; de Vries, J.; Feringa, B. L. Org. Lett. 2003, 5, 475.
    • (h) For ligands 21 and 2m, see: Peña, D.; Minnaard, A. J.; de Vries, A. H. M.; de Vries, J.; Feringa, B. L. Org. Lett. 2003, 5, 475.
  • 50
    • 0001146718 scopus 로고    scopus 로고
    • For ligand 2n, see: Imbos, R.; Brilman, M. H. G.; Pineschi, M.; Feringa, B. L. Org. Lett. 1999, 1, 623.
    • (i) For ligand 2n, see: Imbos, R.; Brilman, M. H. G.; Pineschi, M.; Feringa, B. L. Org. Lett. 1999, 1, 623.
  • 51
    • 39749091476 scopus 로고    scopus 로고
    • General Procedure for the Parallel Synthesis of the Ligands: 21 The amine (0.25 mmol) was added to a carousel tube, followed by Et3N (0.25 mmol, The tube was sealed, flushed with argon and cooled to -40°C A 0.25 M stock solution of BINOL-chlorophosphite (1 mL) in toluene was added, and the reaction was left to warm overnight. The reaction mixture was rapidly filtered through a small plug of silica gel into a new sealed and degassed carousel tube. The filtrate was washed with toluene (1 mL, and the combined toluene solutions of the ligand were used directly in the next step. Spectral Data for Crude 2b: 1H NMR (400 MHz, CDCl 3, δ, 7.80-8.10 (m, 4 H, 7.20-7.60 (m, 12 H, 13C NMR(100 MHz, CDCl3, δ =145.7, 144.9, 132.0, 131.6, 131.5, 128.7, 128.6, 127.3, 127.2, 127.0 (J, 2.3 Hz, 126.2, 126.1, 121.0, 120.2 J, 38 Hz, IR: 1298, 1224, 966, 929, 881, 816, 752 cm -1
    • -1.
  • 53
    • 39749139144 scopus 로고    scopus 로고
    • General Procedure for the Formation of the Intermediate Cobalt Complexes: The propargylic alcohol (1-butyn-3-ol, 6 or 8) was dissolved in CH2Cl2 in a two-necked flask under argon. An equimolar amount of dicobalt octacarbonyl, dissolved in CH2Cl 2, was added. The reaction was protected from light by wrapping the flask in foil, and the solution was stirred at r.t. for 3 h. The mixture was filtered through a short plug of silica, eluting with CH2Cl 2, and concentrated, affording the complex as a dark red oil. The ligand (0.25 mmol) was added to a Radleys carousel tube and dissolved in toluene (1 mL, The tube was sealed and flushed with argon. A 0.125 M stock solution of the alkyne-cobalt complex (1 mL) in toluene was added to the tube. The reaction mixture was heated at 50°C overnight. The solvent was removed in vacuo, and the crude phosphoramidite-cobalt-alkyne complex thus formed was used directl
    • 2, and concentrated, affording the complex as a dark red oil. The ligand (0.25 mmol) was added to a Radleys carousel tube and dissolved in toluene (1 mL). The tube was sealed and flushed with argon. A 0.125 M stock solution of the alkyne-cobalt complex (1 mL) in toluene was added to the tube. The reaction mixture was heated at 50°C overnight. The solvent was removed in vacuo, and the crude phosphoramidite-cobalt-alkyne complex thus formed was used directly in the Nicholas reaction in the same reaction tube.
  • 54
    • 39749102637 scopus 로고    scopus 로고
    • General Procedure for the Asymmetric Nicholas Reaction: The phosphoromidite-cobalt-alkyne complex (0.25 mmol) was dissolved in CH 2Cl2 (1 mL) and cooled to -30°C. BF 3·OEt2 (47.5 μL, 0.375 mmol, was added, followed by the dropwise addition of the nucleophile (0.5 mmol, After 16 h, the reaction was quenched with Et3N (69.7 μL, 0.5 mmol, and the solvent was removed in vacuo. Decomplexation was effected by dissolving the residue in THF-H2O (9:1, cooling to -10°C, followed by the portionwise addition of a 0.18 M solution of cerium ammonium nitrate in THF-H2O (9:1) until the dark red solution turned orange-yellow (the amount of CAN solution used corresponded to approximately 5 equiv in most cases, and up to 10 equiv in a few cases, The reaction mixture was diluted with brine (1 mL) and extracted with Et2O 3 x 2 mL, The combined organic phases were dried over MgSO4
    • 4 and concentrated. The crude product was purified by flash chromatography, eluting with 5-10% EtOAc in PE. The enantioselectivity was measured by HPLC on both the crude and the pure product, using a Daicel Chiralpak AD-H column (hexane-i-PrOH, 95:5).
  • 55
    • 0037037850 scopus 로고    scopus 로고
    • For compound 5, see: Asao, N.; Ohishi, T.; Sato, K.; Yamamoto, Y. Tetrahedron 2002, 58, 8195.
    • (b) For compound 5, see: Asao, N.; Ohishi, T.; Sato, K.; Yamamoto, Y. Tetrahedron 2002, 58, 8195.
  • 56
    • 39749199855 scopus 로고    scopus 로고
    • For compounds 7, 9, 10 and 11, see ref. 4b.
    • (c) For compounds 7, 9, 10 and 11, see ref. 4b.
  • 59
    • 39749201263 scopus 로고    scopus 로고
    • General Procedure for the Preparation of the Precursor Propargylic Alcohols, Exemplified by 6: 4-Iodoacetophenone (500 mg, 2.03 mmol, Pd(PPh3)4 (23.5 mg, 0.020 mmol) and CuI (7.7 mg, 0.040 mmol) were added to a 5-mL microwave reaction tube flushed with argon. Freshly distilled Et3N (2 mL) and anhyd DMF (1 mL) were added, followed by 1-octyn-3-ol (355 μL, 2.43 mmol, The reaction was heated at 100°C for 10 min using a Biotage Initiator microwave reactor. The reaction mixture was then filtered through a pad of Celite, diluted with Et2O and washed with brine. Drying over MgSO4 followed by rotary evaporation afforded 6 (390 mg) as an amber-yellow oil. For larger-scale reactions, the reaction was run with conventional heating at 40°C for 16 h. Data for 6: 1H NMR (400 MHz, CDCl3, δ, 7.87 (d, J, 8.4 Hz, 2 H, 7.48 (d, J, 8.4 Hz, 2 H, 4.56-4.64 (m, 1 H, 2.59 s, 3 H
    • 14O: C, 82.72; H, 8.10. Found: C, 82.65; H, 8.03.
  • 60
    • 39749177457 scopus 로고    scopus 로고
    • Carousel 12 Reaction Station was obtained from Radleys Discovery Technologies.
    • Carousel 12 Reaction Station was obtained from Radleys Discovery Technologies.

* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.