Highly Efficient Oxidative Cleavage of Carbon‐Carbon Double Bond over meso‐Tetraphenyl Cobalt Porphyrin Catalyst in the Presence of Molecular Oxygen

Abstract

Highly efficient and selective carbon-carbon double bond aerobic cleavage of olefins catalyzed by metalloporphyrins was investigated, and carbonyl compounds and epoxide were produced as the main products. CoTPP (cobalt meso-tetraphenyl porphyrin) showed excellent activity for the oxidative cleavage of carbon-carbon double bond by using styrene as model compound, in which the TOF (turnover frequency) and selectivity toward benzaldehyde was obtained with 2×10 4 h -1 and 86%, respectively.

Rhodium(I)‐Catalyzed [4 + 2] Cycloaddition Reactions of 2‐Alkylenecyclo‐butanols with Alkynes and (E)‐2‐Nitroethenylbenzene through C(sp2)—C(sp3) Bond Cleavage

“…(E)-6'-Benzylidene-3'-(but-3-en-1-yl)- 3',4',5',6'-tetrahydro-[1,1':2',1''-terphenyl]-3'-ol (3e) was obtained as yellow oil (36.0 mg, 0.092 mmol, 76%). 1 H NMR (400 MHz, CDCl 3 ) δ: 7.28 (d,J = 7.3 Hz,3H),3H),.93 (m, 9H), 6.01 (s, 1H), 5.77 (dd,J = 17.0,6.7 Hz,1H),4.96 (dd,J = 31.0,13.5 Hz, 2H), 2.99 (s, 1H), 2.86 (d, J = 10.6 Hz, 1H), 2.17 (s, 3H), 2.00 (d, J = 10.5 Hz, 1H), 1.89 (d, J = 10.1 Hz, 1H), 1.64 (d,J = 14.5 Hz,2H). 13 C NMR (101 MHz, CDCl 3 ) δ: 144.…”

“…469. , found 469.1936 was obtained as yellow oil (81.0 mg, 0.18 mmol, 78%). 1 H NMR (400 MHz, CDCl 3 ) δ: 7.61 (d,J = 8.1 Hz,2H),7.22 (d,J = 7.9 Hz,2H),9H),3H),2H),6.13 (s,1H),2.95 (d,J = 16.3 Hz,1H),2.60 (t,J = 14.0 Hz,1H),2.38 (s,3H),2.32 (dd,J = 12.8,3.8 Hz,1H),2.28 (s,3H),2.11 (dd,J = 8.1,4.2 Hz,1H),2.02 (s,1H). 13 C NMR (101 MHz, CDCl 3 ) δ: 142.…”

“…IR (neat) ν: , 1006 '-phenyl-1',4',5',6'-tetrahydro-[1,1':2',1''-terphenyl]-1'-ol (3k) was obtained as yellow oil (90.0 mg, 0.20 mmol, 82%). 1 H NMR (400 MHz, CDCl 3 ) δ: 7.74 (d,J = 7.5 Hz,2H),7.41 (t,J = 7.6 Hz,2H),7.31 (t,J = 7.3 Hz,1H),7H),6.92 (dd,J = 6.9,3.4 Hz,3H),4H),6.11 (s,1H), 3.74 (s,3H),2.95 (dd,J = 12.0,8.0 Hz,1H),2.60 (d,J = 2.4 Hz,1H),1H),2H). 13 C NMR (101 MHz, CDCl 3 ) δ: 158.…”

“…IR (neat) ν: , 10822, 145.6, 141.6, 141.3, 139.6, 138.0, 136.3, 130.8, 130.5, 130.2, 128.1, 127.4, 127.35, 127.2, 126.6, 126.3, 126.2, 113.4, 76.2, 55.2, 39.0, 24.5. IR (neat) ν: , 1030 (d,J = 7.4 Hz,1H),2H),.03 (m, 7H), 6.94 (s, 3H), 6.80 (d, J = 7.5 Hz, 4H), 6.12 (s, 1H), 3.76 (s, 3H), 2.97 (d, J = 16.2 Hz, 1H), 2.60 (t, J = 14.1 Hz, 1H), 2.38-2.31 (m, 1H), 2.12 (d,J = 11.8 Hz,2H). 13 C NMR (101 MHz, CDCl 3 ) δ: 158.…”

“…IR (neat) ν: , 10501, 141.1, 139.8, 139.6, 138.2, 133.7, 130.8, 130.5, 128.0, 127.4, 127.2, 127.0, 126.5, 126.2, 125.9, 76.7, 76.2, 39.0, 37.2, 32.8, 32.3, 26.0, 25.9, 25.8, 22.2. IR (neat) ν: , 1004 (d,J = 11.7 Hz,2H). 13 C NMR (101 MHz, CDCl 3 ) δ: 157.…”