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(Z)-γ-(p-methoxyphenoxy)allyldiisopinocamphenylborane was prepared from (+)-α-pinene according to: H. C. Brown, P. K. Jadhav, K. S. Bhat. J. Am. Chem. Soc. 1988, 110, 1535-1538, and references therein.
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29344432891
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H-5/H-6= 17.0 Hz is typical of an E double bond. The NOESY spectrum showed two positive cross peaks due to scalar coupling (E double bond), instead of two negative cross peaks due to NOE (Z double bond).
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76
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29344440828
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b). The signal of the proton of the trisubstituted double bond (H-6, δ = 5.57 ppm) showed a coupling with the signal at δ= 4.72 ppm (H-7), which, in turn, coupled with the signal at δ= 4.25 ppm (H-8).
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29344454720
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The four low-quality torsional parameters are: two Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)=O(sp2) torsion, ester group] and two H1-C2-C3-O3 [for the H-C(sp2)-C(sp3)-O(sp3) torsion, allylic ethers].
-
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82
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29344469127
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-
note
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The ten low-quality torsional parameters are: two Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)=O(sp2) torsion, ester group], two H1-C2-C3-O3 [for the H-C(sp2)-C(sp3)-O(sp3) torsion, allylic ethers], two 00-C3-O3-00 [for the C(sp2)-C(sp3)-O(sp3)-C(sp2) torsion, allylic phenyl ethers], four Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)= C(sp2) torsion, phenyl ethers].
-
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83
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29344474511
-
-
note
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The six low-quality torsional parameters are: two Lp-O3-C0*00 [for the Lp-O(sp3)-C(sp2)=O(sp2) torsion, ester group], one 00*C2= C2*00 [for the (O=)C-CH=CH-C(=O) torsion, enedione], two 00-C2-C3-00 [for the O(sp3)-C(sp3)-C(sp2)-C(sp2) torsion], one C0-C3-O3-C2 [for the (O=)C-C(sp3)-O(sp3)-C(=O) torsion].
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85
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29344465801
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The Ru atom was substituted with a carbon atom. The "frozen" core structure (corresponding to the original ruthenacyclobutane fragment including the substituents at ruthenium) maintained its initial geometry, while the rest of the structure was smoothly minimized. After the conformational search and the minimization, the Ru atom was reinstalled, and the structures were optimized with the DFT calculations.
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