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Volumn 74, Issue 22, 2009, Pages 8583-8594

Asymmetric synthesis of all-carbon benzylic quaternary stereocenters via conjugate addition to alkylidene and indenylidene Meldrum's acids

Author keywords

[No Author keywords available]

Indexed keywords

ALKYL GROUPS; ALKYLIDENES; ARYL GROUP; ASYMMETRIC SYNTHESIS; BENZYLIC; CHEMICAL EQUATIONS; CONJUGATE ADDITION; DIALKYLZINC REAGENTS; ENANTIOSELECTION; ENANTIOSELECTIVE; HETEROAROMATICS; HIGH ENANTIOSELECTIVITY; MELDRUM'S ACIDS; ORGANOZINC REAGENTS; PATTERN OF SUBSTITUTION; QUATERNARY STEREOCENTERS; SYSTEMATIC STUDY;

EID: 70449713872     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo901559d     Document Type: Article
Times cited : (62)

References (86)
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    • Asymmetric synthesis of tertiary carbon centers from alkylidene Meldrum's acids and dialkylzinc reagents: (a) Knöpfel, T. F.; Zarotti, P.; Ichikawa, T.; Carreira, E. M. J. Am. Chem. Soc. 2005, 127, 9682-9683.
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    • note
    • The absolute stereochemistry of Meldrum's acid 6 was assigned by derivatization to known compounds; see ref 4d.
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    • An interesting observation was made regarding the overall superior electrophilicity of alkylidene Meldrum's acids compared to their structurally similar alkylidene dimethyl malonates. Under conditions in which alkylidene Meldrum's acid 4 is alkylated in > 99%conversion, the analogous alkylidene malonate was inert. For asymmetric 1,4-addition of organozinc or aluminum reagents to alkylidene malonates for the formation of tertiary stereocentres, see: (a)
    • An interesting observation was made regarding the overall superior electrophilicity of alkylidene Meldrum's acids compared to their structurally similar alkylidene dimethyl malonates. Under conditions in which alkylidene Meldrum's acid 4 is alkylated in > 99%conversion, the analogous alkylidene malonate was inert. For asymmetric 1,4-addition of organozinc or aluminum reagents to alkylidene malonates for the formation of tertiary stereocentres, see: (a) Schppan, J.; Minnaard, A. J.; Feringa, B. L. Chem. Commun. 2004, 792-793.
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    • The absolute stereochemistry of 67 was assigned by X-ray crystallography; see the Supporting Information.
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    • note
    • Despite higher catalysts loading, a low 59% conversion was observed.
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    • note
    • The analogous cyclohexyl derivative was also unreactive toward conjugate addition of Et2Zn.
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    • The absolute stereochemistry of 106 was assigned by X-ray crystallography; see the Supporting Information.
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    • note
    • See page 2809 in ref 1d.
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    • This is consistent with published crystallographic data for alkylidene Meldrum's acids. (a) For a recent discussion on Meldrum's acid's boat conformation, see
    • This is consistent with published crystallographic data for alkylidene Meldrum's acids. (a) For a recent discussion on Meldrum's acid's boat conformation, see: Chopra, D.; Zhurov, V. V.; Zhurova, E. A.; Pinkerton, A. A. J. Org. Chem. 2009, 74, 2389-2395.
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    • For a review on the conformation of alkylidene Meldrum's acids and similar derivatives, see
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    • Original structure determination by X-ray crystallography
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    • note
    • The unit cell contains two molecules, thus two sets of data. The dihedral angle C(27)-C(33)-C(34)-C(39) for the second molecule is -100.4°. Bond length C(27)-C(33) is 1.35 Å.
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    • An example of atropoisomerism with alkylidene Meldrum's acid was reported; see
    • An example of atropoisomerism with alkylidene Meldrum's acid was reported; see: Huck, N. P. M.; Meetsma, A.; Zijlstra, R.; Feringa, B. L. Tetrahedron Lett. 1995, 36, 9381-9384.
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    • 2-H(7-position). A persistent, intramolecular C-H⋯X (X = O, S, Br, Cl, and F) hydrogen bond in solution and solid states was previously reported for benzyl Meldrum's acid derivatives; see
    • 2-H(7-position). A persistent, intramolecular C-H⋯X (X = O, S, Br, Cl, and F) hydrogen bond in solution and solid states was previously reported for benzyl Meldrum's acid derivatives; see: Fillion, E.; Wilsily, A.; Fishlock, D. J. Org. Chem. 2009, 74, 1259-1267.
    • (2009) J. Org. Chem. , vol.74 , pp. 1259-1267
    • Fillion, E.1    Wilsily, A.2    Fishlock, D.3


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.