References and Notes
1
The Porphyrin Handbook
Vol. 1-20:
Kadish KM.
Smith KM.
Guilard R.
Academic Press;
San Diego:
2000-2003.
For lead reviews, see:
2a
Sharman WM.
van Lier JE.
J. Porphyrins Phthalocyanines
2000,
4:
441
2b
Setsune J.
J. Porphyrins Phthalocyanines
2004,
8:
93
For selective and recent reports, see:
3a
Liu C.
Shen D.-M.
Chen Q.-Y.
J. Org. Chem.
2007,
72:
2732
3b
Sahoo AK.
Mori S.
Shinokubo H.
Osuka A.
Angew. Chem. Int. Ed.
2006,
45:
7972
3c
Esdaile LJ.
Senge MO.
Arnold DP.
Chem. Commun.
2006,
4192
3d
Shen D.-M.
Liu C.
Chen Q.-Y.
J. Org. Chem.
2006,
71:
6508
3e
Liu C.
Shen D.-M.
Chen Q.-Y.
Eur. J. Org. Chem.
2006,
2703
3f
Takanami T.
Hayashi M.
Chijimatsu H.
Inoue W.
Suda K.
Org. Lett.
2005,
7:
3937
3g
Liu C.
Chen Q.-Y.
Synlett
2005,
8:
1306
3h
Liu C.
Chen Q.-Y.
Eur. J. Org. Chem.
2005,
3680
3i
Gao G.-Y.
Colvin AJ.
Chen Y.
Zhang XP.
J. Org. Chem.
2004,
69:
8886
3j
Gao G.-Y.
Chen Y.
Zhang XP.
Org. Lett.
2004,
6:
1837
3k
Gao G.-Y.
Colvin AJ.
Chen Y.
Zhang XP.
Org. Lett.
2003,
5:
3261
3l
Gao G.-Y.
Chen Y.
Zhang XP.
J. Org. Chem.
2003,
68:
6215
3m
Chen Y.
Zhang XP.
J. Org. Chem.
2003,
68:
4432
3n
Takanami T.
Hayashi M.
Hino F.
Suda K.
Tetrahedron Lett.
2003,
44:
7353
4a
Handbook of Grignard Reagents
Silverman GS.
Rakita PE.
Marcel Dekker;
New York:
1996.
4b
Grignard Reagents: New Developments
Richey HG.
Wiley;
Chichester:
2000.
5a
Rieke RD.
Acc. Chem. Res.
1977,
10:
301
5b
Lee J.-s.
Velarde-Ortiz R.
Guijarro A.
Wurst JR.
Rieke RD.
J. Org. Chem.
2000,
65:
5428
5c
Rieke RD.
Bales SE.
J. Am. Chem. Soc.
1974,
96:
1775
6a
Locos OP.
Arnold DP.
Org. Biomol. Chem.
2006,
4:
902
6b
Hartnell RD.
Edwards AJ.
Arnold DP.
J. Porphyrins Phthalocyanines
2002,
6:
695
7
Typical Procedure for the Grignard Reactions of Bromoporphyrin Ni3 with Ketones or Aldehydes
Freshly cut potassium (65 mg, 20 equiv), MgCl2 (190 mg, 20 equiv), KI (275 mg, 20 equiv), and DME (10 mL) were placed in an oven-dried 50 mL Schlenk flask under N2. The mixture was stirred and heated to reflux for 2 h and cooled to r.t. A DME (20 mL) solution of Ni3 (50 mg, 1.0 equiv)and cyclohexanone (2a, 175 mL, 20 equiv) was then charged with a syringe slowly under N2. After 5 min, the mixture was diluted with CH2Cl2 (30 mL), quenched with sat. NH4Cl solution, and washed with H2O three times. The organic layer was passed through dry silica gel and evaporated to dryness. The resulting solid was purified by flash column chromatography (silica gel, 300-400 mesh, PE-CH2Cl2, 1:1 v/v) to afford Ni4a (33 mg, 65% yield).
Spectroscopy data of Ni4a are as follows: 1H NMR (300 MHz, CDCl3): δ =2.13-2.46 (m, 4 H), 2.79-3.10 (m, 4 H), 5.48-5.54 (m, 1 H), 7.67 (d, J = 5.7 Hz, 9 H), 7.96 (d, J = 6.3 Hz, 6 H), 8.67 (s, 4 H), 8.74 (d, J = 5.1 Hz, 2 H), 8.96 (d, J = 5.1 Hz, 2 H). MS (MALDI): m/z = 690.2 [M+]. UV/Vis (CH2Cl2): λmax (relative intensity) = 416 (14.8), 533 (1.0) nm. Anal. Calcd for C44H32N4NiO×1.5H2O: C, 73.56; H, 4.91; N, 7.80. Found: C, 73.47; H, 4.76; N, 7.52. IR (KBr): 2930, 1710, 1598, 1440, 1349, 1124, 1007, 792, 747, 701 cm-1.
Spectroscopy data of Ni7a are as follows: 1H NMR (300 MHz, CDCl3): δ =3.36 (s, 1 H), 7.26 (3 H, overlapping with the signal of CDCl3), 7.54 (d, J = 6.6 Hz, 2 H), 7.67 (br s, 9 H), 7.97 (br s, 6 H), 8.70 (br s, 6 H), 9.29 (br s, 2 H). MS (MALDI): m/z = 700.2 [M+]. UV/Vis (CH2Cl2) λmax (relative intensity) = 415 (14.7), 529 (1.0) nm. HRMS (MALDI): m/z calcd for C45H30N4NiO+ [M+]: 700.1798; found: 700.1768.
8a
Felkin H.
Gault Y.
Roussi G.
Tetrahedron
1970,
26:
3761
8b
Pinkus AG.
Sabesan A.
J. Chem. Soc., Perkin Trans. 2
1981,
473
8c
Pinkus AG.
Servoss WC.
J. Chem. Soc., Perkin Trans. 2
1979,
1600
8d
Benkeser RA.
Johnston TE.
J. Am. Chem. Soc.
1966,
88:
2220
