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Volumn 133, Issue 16, 2011, Pages 6166-6169

Selective activation of enantiotopic C(sp3)-hydrogen by means of chiral phosphoric acid: Asymmetric synthesis of tetrahydroquinoline derivatives

Author keywords

[No Author keywords available]

Indexed keywords

ASYMMETRIC SYNTHESIS; C-H FUNCTIONALIZATION; SELECTIVE ACTIVATION; TETRAHYDROQUINOLINE;

EID: 79955017892     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja2014955     Document Type: Article
Times cited : (232)

References (82)
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    • These types of reactions have been classified under the term tert -amino effect. For reviews, see: Meth-Cohn, O.; Suschitzky, H. Adv. Heterocycl. Chem. 1972, 14, 211
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    • For reviews of chiral phosphoric acid catalysis, see: Akiyama, T.; Itoh, J.; Fuchibe, K. Adv. Synth. Catal. 2006, 348, 999
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    • For the detailed screening of catalysts and substrates, see the Supporting Information
    • For the detailed screening of catalysts and substrates, see the Supporting Information.
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    • Substrates possessing an N-cyclic moiety such as an isoquinoline, isoindoline, pyrrolidine, or piperidine ring yielded low enantioselectivities (less than 10% ee)
    • Substrates possessing an N-cyclic moiety such as an isoquinoline, isoindoline, pyrrolidine, or piperidine ring yielded low enantioselectivities (less than 10% ee).
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    • Phosphoric acid derivatives 5 and 6 were used after washing with 6 N HCl
    • Phosphoric acid derivatives 5 and 6 were used after washing with 6 N HCl.
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    • The absolute configuration of (S)- 8 was determined by X-ray analysis of the corresponding monobrominated product s30. For more details, see the Supporting Information
    • The absolute configuration of (S)- 8 was determined by X-ray analysis of the corresponding monobrominated product s30. For more details, see the Supporting Information.
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    • In the 1980s, the Reinhoudt group found the thermal version of the highly stereoselective internal redox reaction. In their case, the chiral information of the starting material was completely converted into the cyclized product. For more details, see refs 3e, 4c, and 4g
    • In the 1980s, the Reinhoudt group found the thermal version of the highly stereoselective internal redox reaction. In their case, the chiral information of the starting material was completely converted into the cyclized product. For more details, see refs 3e, 4c, and 4g.
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    • This kind of asymmetric transformation is recognized as memory of chirality . For leading references, see: Kawabata, T.; Yahiro, K.; Fuji, K. J. Am. Chem. Soc. 1991, 113, 9694
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    • The significant decrease in the enantioselectivity when (R)- 7 was used implies the existence of matched and mismatched modes in the cyclization step. The reason for this stereomutation is unclear and under investigation
    • The significant decrease in the enantioselectivity when (R)- 7 was used implies the existence of matched and mismatched modes in the cyclization step. The reason for this stereomutation is unclear and under investigation.
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    • Treatment of (S)- 7 with rac -binaphthyl phosphoric acid 6a afforded (S)- 8 with 85% ee, although the chemical yield was low (15%). We also tried the achiral acid catalyst (biphenyl phosphoric acid). Although high temperature and a longer reaction time were required (in toluene at refluxing temperature for 68 h), the stereochemical information was retained at an acceptable level. The cyclized adduct (S)-8 was obtained with 54% ee in 40% chemical yield. For more details, see the Supporting Information
    • Treatment of (S)- 7 with rac -binaphthyl phosphoric acid 6a afforded (S)- 8 with 85% ee, although the chemical yield was low (15%). We also tried the achiral acid catalyst (biphenyl phosphoric acid). Although high temperature and a longer reaction time were required (in toluene at refluxing temperature for 68 h), the stereochemical information was retained at an acceptable level. The cyclized adduct (S)-8 was obtained with 54% ee in 40% chemical yield. For more details, see the Supporting Information.
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    • Seidel (10a) and Feng (10c) proposed that enantiofacial selection of the iminium cation is the key factor leading to the high enantioselectivity
    • Seidel (10a) and Feng (10c) proposed that enantiofacial selection of the iminium cation is the key factor leading to the high enantioselectivity.
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    • The key [1,5]-hydride shift took place suprafacially. For more details, see refs 4c and 4g and references cited therein
    • The key [1,5]-hydride shift took place suprafacially. For more details, see refs 4c and 4g and references cited therein.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.