Mapping the PES of the Tolylcarbene Rearrangement
A R T I C L E S
Acetal C-H Insertion Product (14). 1H NMR (400 MHz; CDCl3;
23 °C): δ 7.30-7.12 (m, 40H), 6.90 (s, 8H, aryl-H), 6.07 (t, 1H, J )
4 Hz, CH2-CHOO), 5.80 (d, 1H, J ) 6.8 Hz, OCHHouterO), 5.73 (d,
1H, J ) 7.2 Hz, OCHHouterO), 5.72 (d, 1H, J ) 7.6 Hz, OCHHouterO),
5.59 (d, 2H, J ) 7.2 Hz, tolyl-H), 5.57 (d, 2H, J ) 6.8 Hz,
OCHHouterO), 5.07 (d, 2H, J ) 7.2 Hz, tolyl-H), 5.00 (t, 1H, J ) 7.6
Hz, Hmethine), 4.97 (t, 1H, J ) 8.4 Hz, Hmethine), 4.91 (t, 2H, J ) 8 Hz,
J ) 8.4 Hz, Hmethine), 4.93 (d, 1H, J ) 6.8 Hz, OCHHouterO), 4.91 (t,
1H, J ) 7.8 Hz, Hmethine), 4.85 (t, 1H, J ) 8.0 Hz, Hmethine), 4.70 (t, 1H,
J ) 8.0 Hz, Hmethine), 4.67 (d, 1H, J ) 7.6 Hz, OCHHinnerO), 4.66 (t,
1H, J ) 8.4 Hz, Hmethine), 4.55 (dd, 1H, J ) 5.4, 9.4 Hz, Hmethine), 4.49
(d, 1H, J ) 6.6 Hz, OCHHinnerO), 4.45 (d, 1H, J ) 7.0 Hz, OCHHinnerO),
4.32-4.20 (m, 2H, O-CH2-CH2), 4.18 (d, 1H, J ) 7.4 Hz,
OCHHinnerO), 4.12 (d, 1H, J ) 7.2 Hz, OCHHinnerO), 4.10 (d, 1H, J )
6.8 Hz, OCHHinnerO), 3.84 (d, 1H, J ) 6.8 Hz, OCHHinnerO), 3.62 (d,
1H, J ) 7.2 Hz, OCHHinnerO), 4.16-3.62 (m, 12H, O-CH2-CH2),
3.48-3.41 (m, 2H, O-CH2-CH2), 2.80-1.60 (m, 48H, CH2CH2Ph,
O-CH2-CH2), -0.69 (s, 1H, CHcyclopropyl), -1.38 (s, 3H, CH3). HR-
MALDI-TOF MS: [M + Na]+, C152H144O24Na calcd 2375.994; found
2376.007. Elemental analysis calcd (%) for C152H144O24: C, 77.53; H,
6.17. Found: C, 77.38; H, 6.16.
Hmethine), 4.79 (t, 1H, J ) 8 Hz, Hmethine), 4.77 (t, 2H, J ) 8 Hz, Hmethine),
4.67 (t, 1H, J ) 7.6 Hz, Hmethine), 4.51 (d, 1H, J ) 6.8 Hz, OCHHinnerO),
4.49 (d, 1H, J ) 7.2 Hz, OCHHinnerO), 4.18 (d, 1H, J ) 7.2 Hz,
OCHHinnerO), 4.14-4.08 (m, 2H, O-CH2-CH2), 4.05-3.90 (m, 12H,
O-CH2-CH2), 4.00 (d, 2H, J ) 6.8 Hz, OCHHinnerO), 3.88-3.81 (m,
2H, O-CH2-CH2), 3.74 (d, 2H, J ) 6.8 Hz, OCHHinnerO), 2.80-2.45
(m, 32H, CH2CH2Ph), 2.12 (sb, 2H, tolyl-CH2), 2.00-1.75 (m, 16H,
OCH2CH2), -0.36 (sb, 3H, CH3). HR-MALDI-TOF MS: [M + Na]+,
1
d48-Aryl Addition Product (d48-16). H NMR (400 MHz; CDCl3;
C
152H144O24Na calcd 2375.994; found 2376.006. Elemental analysis
23 °C): δ 7.30-7.08 (m, 40H), 6.95 (s, 1H, aryl-H), 6.93 (s, 1H,
aryl-H), 6.92 (s, 2H, aryl-H), 6.89 (s, 1H, aryl-H), 6.78 (s, 1H, aryl-
H), 6.65 (s, 1H, aryl-H), 6.00 (d, 2H, J ) 8 Hz, tolyl-H), 5.95 (s,
1H, CHvinyl), 5.58 (d, 2H, J ) 8 Hz, tolyl-H), 5.07 (t, 1H, J ) 7.6 Hz,
calcd (%) for C152H144O24: C, 77.53; H, 6.17. Found: C, 77.58; H,
6.16.
1
d48-Acetal C-H Insertion Product (d48-14). H NMR (400 MHz;
H
methine), 4.98 (t, 1H, J ) 8 Hz, Hmethine), 4.94 (t, 1H, J ) 8 Hz, Hmethine),
CDCl3; 23 °C): δ 7.30-7.12 (m, 40H), 6.90 (s, 8H, aryl-H), 5.59 (d,
2H, J ) 8 Hz, tolyl-H), 5.08 (d, 2H, J ) 8 Hz, tolyl-H), 4.99 (t, 1H,
J ) 7.6 Hz, Hmethine), 4.97 (t, 1H, J ) 8.4 Hz, Hmethine), 4.91 (t, 2H,
J ) 7.2 Hz, Hmethine), 4.79 (t, 1H, J ) 8 Hz, Hmethine), 4.77 (t, 2H, J )
8 Hz, Hmethine), 4.67 (t, 1H, J ) 7.6 Hz, Hmethine), 2.80-2.44 (m, 32H,
CH2CH2Ph), 2.12 (sb, 1H, tolyl-CHD), -0.36 (sb, 3H, CH3). HR-
MALDI-TOF MS: [M + Na]+, C152H96D48O24Na calcd 2424.290; found
2424.297.
4.91 (t, 1H, J ) 7.2 Hz, Hmethine), 4.84 (t, 1H, J ) 8.0 Hz, Hmethine),
4.69 (t, 1H, J ) 8.0 Hz, Hmethine), 4.65 (t, 1H, J ) 8 Hz, Hmethine), 4.55
(dd, 1H, J ) 5.4, 10 Hz, Hmethine), 2.90-2.25 (m, 32H, CH2CH2Ph),
-0.67 (s, 1H, CHcyclopropyl), -1.39 (s, 3H, CH3). HR-MALDI-TOF
MS: [M + Na]+, C152H96D48O24Na calcd 2424.290; found 2424.268.
Aryl Addition Product (17). This was isolated as a 4:1 mixture
1
with the C-O insertion product 15. H NMR (400 MHz; CDCl3; 23
C-O Insertion Product (15). 1H NMR (400 MHz; CDCl3; 23
°C): δ 7.25-7.10 (m, 40H), 6.93 (s, 1H, aryl-H), 6.90 (s, 2H, aryl-
H), 6.86 (s, 1H, aryl-H), 6.85 (s, 1H, aryl-H), 6.78 (s, 1H, aryl-H),
6.77 (s, 2H, aryl-H), 6.19 (d, 2H, J ) 6.8 Hz, tolyl-H), 6.00 (d, 1H,
J ) 6.8 Hz, OCHHouterO), 5.95 (d, 1H, J ) 7.0 Hz, OCHHouterO), 5.90
(d, 1H, J ) 6.8 Hz, OCHHouterO), 5.86 (d, 2H, J ) 6.8 Hz, tolyl-H),
5.82 (d, 1H, J ) 6.4 Hz, OCHHouterO), 5.76 (d, 1H, J ) 6.4 Hz,
OCHHouterO), 5.70 (d, 1H, J ) 6.8 Hz, OCHHouterO), 5.67 (d, 1H, J )
6.8 Hz, OCHHouterO), 5.60 (d, 1H, J ) 6.6 Hz, OCHHouterO), 5.00 (t,
1H, J ) 7.6 Hz, Hmethine), 4.96 (d, 1H, J ) 6.4 Hz, OCHHinnerO), 4.96
(t, 1H, J ) 8.0 Hz, Hmethine), 4.92 (t, 1H, J ) 8.0 Hz, Hmethine), 4.91 (t,
1H, J ) 8.0 Hz, Hmethine), 4.90 (t, 1H, J ) 8.0 Hz, Hmethine), 4.80 (t, 1H,
J ) 8.0 Hz, Hmethine), 4.76 (t, 1H, J ) 8.0 Hz, Hmethine), 4.74 (t, 1H,
J ) 8.0 Hz, Hmethine), 4.73 (d, 1H, J ) 6.8 Hz, OCHHinnerO), 4.69 (t,
1H, J ) 8.0 Hz, Hmethine), 4.68 (t, 1H, J ) 8.0 Hz, Hmethine), 4.49 (d,
1H, J ) 6.8 Hz, OCHHinnerO), 4.45 (d, 1H, J ) 7.0 Hz, OCHHinnerO),
4.48-4.40 (m, 1H, O-CH2-CH2), 4.23 (d, 1H, J ) 6.8 Hz,
OCHHinnerO), 4.32-4.14 (m, 6H, O-CH2-CH2), 4.09-3.94 (m, 6H,
O-CH2-CH2), 4.01 (d, 1H, J ) 6.8 Hz, OCHHinnerO), 3.94-3.84 (m,
1H, O-C(Ph)H-CH2), 3.81-3.74 (m, 1H, O-CH2-CH2), 3.73 (d,
1H, J ) 6.6 Hz, OCHHinnerO), 3.59 (d, 1H, J ) 6.6 Hz, OCHHinnerO),
2.80-2.40 (m, 32H, CH2CH2Ph), 2.22-1.76 (m, 14H, CH2CH2CH2-
CH2), 1.60-1.53 (m, 1H, OCH(Ph)-CH2CH2CHH-CH2O), 1.52-1.48
(m, 1H, OCH(Ph)-CHHCH2CH2-CH2O), 1.40-1.34 (m, 1H, OCH-
(Ph)-CH2CHHCH2CH2O), 1.10-1.00 (m, 1H, OCH(Ph)-CHHCH2-
CH2-CH2O), -0.31 (sb, 3H, CH3). HR-MALDI-TOF MS: [M + Na]+,
°C): δ 7.32-7.02 (m, 40H), 7.00 (s, 1H, aryl-H), 6.95 (s, 1H, aryl-
H), 6.93 (s, 2H, aryl-H), 6.92 (s, 2H, aryl-H), 6.90 (s, 1H, aryl-H),
6.89 (s, 1H, aryl-H), 6.82 (s, 1H, aryl-H), 6.35 (d, 2H, J ) 7.6 Hz,
tolyl-H), 6.02 (d, 1H, J ) 7.2 Hz, OCHHouterO), 5.91 (d, 1H, J ) 7.2
Hz, OCHHouterO), 5.88 (d, 2H, J ) 7.6 Hz, tolyl-H), 5.86 (d, 1H, J )
7.6 Hz, OCHHouterO), 5.81 (d, 1H, J ) 6.8 Hz, OCHHouterO), 5.42 (d,
1H, J ) 7.2 Hz, OCHHouterO), 5.27 (d, 1H, J ) 8 Hz, OCHHouterO),
5.26 (d, 1H, J ) 8 Hz, OCHHouterO), 5.25 (s, 1H, CHvinyl), 5.23 (d, 1H,
J ) 6.8 Hz, OCHHouterO), 4.95 (t, 1H, J ) 8 Hz, Hmethine), 4.93 (t, 1H,
J ) 8 Hz, Hmethine), 4.90 (t, 1H, J ) 8 Hz, Hmethine), 4.89 (t, 1H, J ) 7.2
Hz, Hmethine), 4.87 (d, 1H, J ) 7.2 Hz, OCHHinnerO), 4.79 (t, 1H, J )
8 Hz, Hmethine), 4.72 (d, 1H, J ) 6.8 Hz, OCHHinnerO), 4.69 (t, 1H, J )
8 Hz, Hmethine), 4.60 (d, 1H, J ) 7.2 Hz, OCHHinnerO), 4.52 (d, 1H,
J ) 7.2 Hz, OCHHinnerO), 4.47 (d, 1H, J ) 7.2 Hz, OCHHinnerO), 4.43
(d, 1H, J ) 7.2 Hz, OCHHinnerO), 4.41-3.90 (m, 12H, OCH2CH2),
3.99 (t, 1H, J ) 8 Hz, Hmethine), 3.72-3.64 (m, 2H, OCH2CH2), 3.68
(t, 1H, J ) 8.4 Hz, Hmethine), 3.58-3.52 (m, 1H, OCH2CH2), 3.50 (d,
1H, J ) 6.8 Hz, OCHHinnerO), 3.30-3.24 (m, 1H, OCH2CH2), 3.29
(d, 1H, J ) 8 Hz, OCHHinnerO), 3.08 (s, 1H, CHcyclopropyl), 2.94-2.40
(m, 32H, CH2CH2Ph), 2.38-1.60 (m, 16H, OCH2CH2), -1.07 (s, 3H,
CH3). HR-MALDI-TOF MS: [M + Na]+, C152H144O24Na calcd
2375.994; found 2375.995. Elemental analysis calcd (%) for C152H144O24‚
CHCl3: C, 74.27; H, 5.91. Found: C, 74.04; H, 5.97.
1
d48-Aryl Addition Product (d48-17). H NMR (400 MHz; CDCl3;
23 °C): δ 7.32-7.02 (m, 40H), 7.01 (s, 1H, aryl-H), 6.95 (s, 1H,
aryl-H), 6.93 (s, 2H, aryl-H), 6.92 (s, 2H, aryl-H), 6.90 (s, 1H, aryl-
H), 6.89 (s, 1H, aryl-H), 6.82 (s, 1H, aryl-H), 6.35 (d, 2H, J ) 8.2
Hz, tolyl-H), 5.88 (d, 2H, J ) 8.2 Hz, tolyl-H), 5.26 (s, 1H, CHvinyl),
4.95 (t, 1H, J ) 8.4 Hz, Hmethine), 4.93 (t, 1H, J ) 8 Hz, Hmethine), 4.90
(t, 1H, J ) 8 Hz, Hmethine), 4.89 (t, 1H, J ) 8 Hz, Hmethine), 4.79 (t, 1H,
J ) 8.4 Hz, Hmethine), 4.68 (t, 1H, J ) 7.6 Hz, Hmethine), 3.99 (t, 1H,
J ) 8 Hz, Hmethine), 3.67 (t, 1H, J ) 8.4 Hz, Hmethine), 3.08 (s, 1H,
CHcyclopropyl), 2.92-2.05 (m, 32H, CH2CH2Ph), -1.07 (s, 3H, CH3).
HR-MALDI-TOF MS: [M + Na]+, C152H96D48O24Na calcd 2424.290;
found 2424.265.
C
152H144O24Na calcd 2375.994; found 2376.007. Elemental analysis
calcd (%) for C152H144O24‚3H2O: C, 75.79; H, 6.03. Found: C, 75.68;
H, 5.99.
Aryl Addition Product (16). 1H NMR (400 MHz; CDCl3; 23 °C):
δ 7.28-7.08 (m, 40H), 6.96 (s, 1H, aryl-H), 6.93 (s, 1H, aryl-H),
6.93 (s, 1H, aryl-H), 6.91 (s, 1H, aryl-H), 6.89 (s, 1H, aryl-H), 6.78
(s, 1H, aryl-H), 6.65 (s, 1H, aryl-H), 6.00 (d, 2H, J ) 8 Hz, tolyl-
H), 5.95 (s, 1H, CHvinyl), 5.89 (d, 1H, J ) 7.0 Hz, OCHHouterO), 5.85
(d, 1H, J ) 7.2 Hz, OCHHouterO), 5.82 (d, 1H, J ) 6.8 Hz, OCHHouterO),
5.75 (d, 1H, J ) 7.6 Hz, OCHHouterO), 5.73 (d, 1H, J ) 7.4 Hz,
OCHHouterO), 5.58 (d, 2H, J ) 8 Hz, tolyl-H), 5.54 (d, 1H, J ) 6.6
Hz, OCHHouterO), 5.33 (d, 1H, J ) 7.2 Hz, OCHHouterO), 5.07 (t, 1H,
J ) 7.6 Hz, Hmethine), 4.98 (t, 1H, J ) 7.6 Hz, Hmethine), 4.94 (t, 1H,
Hemicarceplex d48-5.C6D5CD3. This was formed upon exposure
of a solution containing d48-5.3b at room temperature to oxygen.
Isolation of d48-5.C6D5CD3 was achieved through preparative TLC
on silica gel plates using CH2Cl2 as mobile phase. 1H NMR (400 MHz;
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J. AM. CHEM. SOC. VOL. 125, NO. 4, 2003 985