Catalytic enantioselective Negishi reactions of racemic secondary benzylic halides

Journal of the American Chemical Society

Volumn 127, Issue 30, 2005, Pages 10482-10483

  Arp, Forrest O ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

BENZYL DERIVATIVE; HALIDE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL BOND; CHEMICAL REACTION; CROSS COUPLING REACTION; DIASTEREOISOMER; ENANTIOSELECTIVITY; REACTION ANALYSIS;

ALKYLATION; BENZYL COMPOUNDS; CATALYSIS; HYDROCARBONS, BROMINATED; STEREOISOMERISM;

EID: 23044496800     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja053751f     Document Type: Article

References (29)

1. For recent reviews, see the following: (a) Metal-catalyzed cross-coupling reactions of unactivated alkyl halides: Frisch, A. C.; Beller, M. Angew. Chem., Int. Ed. 2005, 44, 674-688.
2. (b) Nickel-catalyzed couplings of unactivated alkyl electrophiles: Netherton, M. R.; Fu, G. C. Adv. Synth. Catal. 2004, 346, 1525-1532.
3. Fischer, C.; Fu, G. C. J. Am. Chem. Soc. 2005, 127, 4594-4595.
4. For a few examples, see: (a) Tamao, K.; Sumitani, K.; Kumada, M. J. Am. Chem. Soc. 1972, 94, 4374-4376.
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7. Our current hypothesis is that the benzylic halide is transformed into a benzylic radical, which then combines with nickel to generate a benzylnickel intermediate.
8. 2·diglyme (35.3 mg, 0.100 mmol), (S)-(i-Pr)-Pybox (39.2 mg, 0.130 mmol), and the benzylic halide (1.00 mmol). The vial was fitted with a septum cap and purged with argon for 15 min. DMA (1.75 mL) was added, and the resulting orange mixture was placed in a 0 °C bath and stirred for 15 min. The organozinc reagent (1.6 M in DMA; 1.0 mL, 1.6 mmol) was added in a single portion, and the resulting homogeneous brown solution was stirred at 0 °C for 24 h. Then, the remaining organozinc reagent was quenched by the addition of ethanol (0.3 mL), and the resulting orange solution was purified directly by flash chromatography.
9. Notes: (a) Use of a commercially available organozinc reagent (Aldrich) led to a lower enantiomeric excess and yield. We recommend that organozinc reagents be prepared from the corresponding alkyl bromides according to the straightforward procedure of Huo: Huo, S. Org. Lett. 2003, 5, 423-425.
10. 2·diglyme.
11. (c) Under our standard conditions, we cannot effectively (yield and/or ee) cross-couple 1,3-dibromoindane, 1-bromotetralin, benzylzincs, or arylzincs.
12. The product of the Negishi reaction depicted in entry 4 (Table 1) has been used as an intermediate in the synthesis of selective δ ligands: Berardi, F.; Ferorelli, S.; Colabufo, N. A.; Leopolde, M.; Perrone, R.; Tortorella, V. Bioorg. Med. Chem. Lett. 2001, 9, 1325-1335.
13. The product of the coupling illustrated in entry 10 (Table 1) has been employed in the total synthesis of natural products such as (+)-nuciferol and (+)-nuciferal. The two previous routes to this compound proceeded in 13 steps from mannitol (Takano, S.; Goto, E.; Ogasawara, K. Tetrahedron Lett. 1982, 23, 5567-5570)
14. and 9 steps from trans-2-butene-1,4-diol (Takano, S.; Sugihara, T.; Samizu, K.; Akiyama, M.; Ogasawara, K. Chem. Lett. 1989, 1781-1784).
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29. To the best of our knowledge, this is the first synthesis of enantioenriched trans-1,3-dimethylindane.