کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1345111 980179 2008 13 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Synthesis of novel C2-symmetric 1,3-bis{(1S,2R,3S,4R)-1,7,7-trimethyl-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzoimidazolium tetrafluoroborates
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Synthesis of novel C2-symmetric 1,3-bis{(1S,2R,3S,4R)-1,7,7-trimethyl-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzoimidazolium tetrafluoroborates
چکیده انگلیسی

Two new C2-symmetric benzoimidazolium tetrafluoroborates 19 and 20 were prepared from (1S)-(+)-camphorquinone 1 in seven and eight steps, respectively. Thus, N1-((1S,2R,3S,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl)benzene-1,2-diamine 11, available in three steps from 1, was first condensed with 1 to afford amino imines 12 and 13/13′. [3 + 2] Cycloaddition of trimethylenemethane (TMM) to 12 or 13/13′ gave cycloadduct 17, which was successfully reduced to diamine 4 using NaCNBH3. Catalytic hydrogenation of methylene groups of 4 gave the methyl analogue 18. Finally, cyclization of diamines 4 and 18 with triethyl orthoformate furnished the desired C2-symmetric benzoimidazolium tetrafluoroborates 19 and 20, respectively. The structures were determined by NMR techniques, NOESY spectroscopy, and X-ray diffraction.

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(1S,4R)-1,11,11-Trimethyl-1,2,3,4-tetrahydro-1,4-methanophenazineC16H18N2De = 100%[α]58921=-29.0 (c 0.30, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: (1S,4R)

N1-[(1S,3E,4R)-2-Oxo-1,7,7-trimethylbicyclo[2.2.1]hept-3-ylidene]-N2-{(1S,2R,3S,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzene-1,2-diamineC30H40N2O2De = 100%[α]58918=-854.4 (c 0.09, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: N1-(1S,3E,4R)1-N2-(1S,2R,3S,4R)

N1-[(1S,3S,4R)-2-Oxo-1,7,7-trimethylbicyclo[2.2.1]hept-3-yl]-N2-{(1S,2R,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-ylidene}benzene-1,2-diamineC30H40N2O2De = 46%[α]58918=-11.3 (c 0.20, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: N1-(1S,3S,4R)-N2-(1S,2R,4R)

N1-[(1S,3R,4R)-2-Oxo-1,7,7-trimethylbicyclo[2.2.1]hept-3-yl]-N2-{(1S,2R,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-ylidene}benzene-1,2-diamineC30H40N2O2De = 100%[α]58918=-71.9 (c 0.21, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: N1-(1S,3R,4R)-N2-(1S,2R,4R)

N1-{(1S,2R,3S,4R)-1,7,7-Trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}-N2-{(1S,2R,3E,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-ylidene}benzene-1,2-diamineC34H46N2O2De = 100%[α]58918=-115.0 (c 0.21, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: N1-(1S,2R,3S,4R)-N2-(1S,2R,3E,4R)

N1-[(1S,3S,4R)-2-Oxo-1,7,7-trimethylbicyclo[2.2.1]hept-3-yl]-N2-{(1S,2R,3S,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzene-1,2-diamineC30H42N2O2De = 100%[α]58921=+42.2 (c 0.06, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: N1-(1S,3S,4R)-N2-(1S,2R,3S,4R)

N1,N2-Bis{(1S,2R,3S,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzene-1,2-diamineC34H48N2O2De = 100%[α]58922=+189.0 (c 0.17, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: bis(1S,2R,3S,4R)

N1,N2-Bis{(1S,2R,3S,4R,4′R)-1,4′,7,7-tetramethyldihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}benzene-1,2-diamineC34H52N2O2De = 100%[α]58921=+93.1 (c 0.12, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: bis(1S,2R,3S,4R,4′R)

1,3-Bis{(1S,2R,3S,4R)-1,7,7-trimethyl-4′-methylenedihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}-1H-benzo[d]imidazol-3-ium tetrafluoroborateC35H47BF4N2O2De = 100%[α]58923=+64.8 (c 0.23, CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: bis(1S,2R,3S,4R)

1,3-Bis{(1S,2R,3S,4R,4′R)-1,4′,7,7-tetramethyldihydro-3′H-spiro[bicyclo[2.2.1]heptane-2,2′-furan]-3-yl}-1H-benzo[d]imidazol-3-ium tetrafluoroborateC35H41BF4N2O2De = 100%[α]58922=+54.7 (c 0.09 CHCl3)Source of chirality: (1S)-(+)-camphorquinoneAbsolute configuration: bis(1S,2R,3S,4R,4′R)

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Tetrahedron: Asymmetry - Volume 19, Issue 3, 19 February 2008, Pages 330–342
نویسندگان
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