Optically active polycarbonates: Asymmetric alternating copolymerization of cyclohexene oxide and carbon dioxide [4]

Journal of the American Chemical Society

Volumn 121, Issue 47, 1999, Pages 11008-11009

  Nozaki, Kyoko ^a   Nakano, Koji ^a   Hiyama, Tamejiro ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CARBON DIOXIDE; CYCLOHEXENE DERIVATIVE; POLYCARBONATE;

CHEMICAL STRUCTURE; CHIRALITY; LETTER; OPTICAL ROTATION; POLYMERIZATION; REACTION ANALYSIS; SYNTHESIS;

EID: 0033485737     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992433b     Document Type: Letter

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30. The sample of run 6, (R,R)-3a with 70% ee, is an 85:15 mixture of (R,R)-3a and (S,S)-3a. On the basis of 94% yield of 3a from 2a, one might assume that the unrecovercd diol units (corresponds to 6%) are all the minor enantiomer, (S,S)-3a. In this case, the enantiomeric excess of the diol unit in 2a would be at least {85 × 0.94 - (15 × 0.94 + 6)}/{85 × 0.94 + ( 15 × 0.94 + 6)} × 100 = 60% ee, corresponding to (R,R):(S,S) = 80:20. Thus, if all the (S,S)-diol unit is involved in syndiotactic diads, (i) the possible maximum content of the syndiotactic diad would be 40%, and (ii) the possible minimum content of the isotactic diad would be 60%. The values contradict the 83:17 of the syndio:iso ratio derived from the literature assignment.
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