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This "chain-segment-mediated stereocontrol" is to be distinguished from "chain-end stereocontrol", the latter being derived from alternative configurations of the last-inserted unit, the former from its spatial orientation.
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Different gauche effects caused by the unequal configurations of the flanking CHD groups are the most likely cause of this difference.
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50
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Dissertation, Universität Freiburg
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2CH-(H,D): Alelyunas. Y. W.; Guo, Z.; LaPointe. R. E.; Jordan, R. F. Organometallics 1993, 12, 544. Related isotope effects: Evans, J.; Schwartz, J.; Urquhart, P. W., J. Organomet. Chem. 1974, 81, C37. Alibrandi, G.; Scolaro, L. M.; Minniti, D.; Romeo, R. Inorg. Chem. 1990, 29, 3467. Negishi, E. I; Nguyen, T.; Maye, J. P. Choueiri, D. Suzuki, N.; Takahashi, T. Chem. Lett. 1992, 2367.
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10244254193
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note
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We find no signs that extra D atoms would be incorporated into position 2 of the n-propyl end group by Zr-D units arising from abstraction of β-D atoms.
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67
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10244265070
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-
note
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sel make any additional contributions to the formation of C negligeable.
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68
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0009537702
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2D signal is apparent above the detection limit of ca. 2-3%. (36) That a metal can traverse between alkene enantiofaces without dissociation has been observed in chiral rhenium olefin complexes (Peng, T.-S.; Gladysz, J. A. J. Am. Chem. Soc. 1992, 114, 4174), but this isomerization requires many hours even at elevated temperatures.
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83
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10244279515
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-
note
-
3 signal.
-
-
-
-
84
-
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10244269300
-
-
note
-
A COSY spectrum also shows cross signals for the protons at 2.06 and 1.69 ppm with those at 4.64 and 4.72 ppm.
-
-
-
-
85
-
-
10244221400
-
-
note
-
4 solutions, these resonances are shifted to higher fields by ca. 0.08 ppm.
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