“On Water” Organocatalyzed [4 + 2] Cycloaddition of Enones and Nitro Dienes for the Enantioselective Synthesis of Densely Substituted Cyclohexanones
Vamisetti, Ganga B.; Chowdhury, Raghunath; Kumar, Mukesh; Ghosh, Sunil K.; Organic Letters  (2016) –; doi:10.1021/acs.orglett.6b00460

data_1543154
_publ_section_title
;
 &#x201C;On Water&#x201D; Organocatalyzed [4 + 2] Cycloaddition of Enones
 and Nitro Dienes for the Enantioselective Synthesis of Densely
 Substituted Cyclohexanones
;
_journal_name_full               'Organic Letters'
_journal_paper_doi               10.1021/acs.orglett.6b00460
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H18 Br N O3'
_chemical_formula_sum            'C20 H18 Br N O3'
_chemical_formula_weight         400.26
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-01-28
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 99.635(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.9479(5)
_cell_length_b                   12.3464(13)
_cell_length_c                   12.9363(12)
_cell_measurement_reflns_used    1846
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      60.8700
_cell_measurement_theta_min      3.4510
_cell_volume                     936.58(15)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
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;
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omega____ theta____ kappa____ phi______ frames
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  2 omega   34.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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  3 omega -114.00  -84.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      -54.7289  -95.0000 -180.0000 30

  4 omega -142.00  -82.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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  5 omega -148.00 -117.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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  6 omega -154.00 -104.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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  7 omega  103.00  141.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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  8 omega   34.00  112.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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  9 omega    7.00   36.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 10 omega   33.00   71.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 11 omega   12.00   65.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577  -25.0000  -60.0000 53

 12 omega   86.00  158.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577  112.0000 -120.0000 72

 13 omega   15.00   41.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 14 omega   41.00  151.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 15 omega    6.00   58.00   1.0000    3.8800
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 16 omega  133.00  158.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 17 omega   83.00  126.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 18 omega   61.00  104.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 19 omega   20.00   65.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 20 omega  -20.00    7.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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 21 omega -149.00 -118.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 22 omega   70.00  112.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 23 omega   17.00   43.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 24 omega   16.00   53.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 25 omega  111.00  158.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 26 omega   45.00   71.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 27 omega   45.00   95.00   1.0000    1.0000
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 28 omega   47.00   73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
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 29 omega   76.00  102.00   1.0000    1.0000
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 30 omega -145.00 -112.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      -54.7289  -61.0000   90.0000 33

 31 omega  -75.00  -14.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      -54.7289  -61.0000   90.0000 61

 32 omega -113.00  -87.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      -54.7289 -125.0000  -60.0000 26

 33 omega -126.00 -100.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      -54.7289  -95.0000  -30.0000 26

 34 omega -141.00 -115.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      -54.7289 -125.0000  -60.0000 26

 35 omega -101.00  -75.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 36 omega -157.00 -131.00   1.0000    3.8800
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    -      -54.7289 -125.0000 -120.0000 26

 37 omega   82.00  117.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -       54.7289  125.0000   60.0000 35

 38 omega  128.00  154.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -       54.7289  125.0000   60.0000 26

 39 omega   78.00  104.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577  -77.0000  -99.0000 26

 40 omega  121.00  158.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577   38.0000 -180.0000 37

 41 omega   79.00  115.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577  112.0000   60.0000 36

 42 omega   52.00  100.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577   38.0000 -150.0000 48

 43 omega   53.00   79.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577   38.0000 -180.0000 26

 44 omega  116.00  154.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577   38.0000  -60.0000 38

 45 omega  103.00  145.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 46 omega   57.00   86.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577   50.0000   60.0000 29

 47 omega   86.00  113.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 48 omega  131.00  157.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 49 omega   94.00  120.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 50 omega   13.00   39.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 51 omega  118.00  144.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
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 52 omega   57.00  107.00   1.0000    3.8800
omega____ theta____ kappa____ phi______ frames
    -      109.4577   38.0000    0.0000 50
;
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_diffrn_measurement_method       '\w scans'
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_diffrn_orient_matrix_UB_12      0.0834191000
_diffrn_orient_matrix_UB_13      0.0808191000
_diffrn_orient_matrix_UB_21      -0.0859646000
_diffrn_orient_matrix_UB_22      -0.0635774000
_diffrn_orient_matrix_UB_23      0.0881167000
_diffrn_orient_matrix_UB_31      0.2207403000
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_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
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_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            6630
_diffrn_reflns_point_group_measured_fraction_full 0.983
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.153
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_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.138
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46728
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.419
_exptl_crystal_description       plate
_exptl_crystal_F_000             408
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.355
_refine_diff_density_min         -0.466
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 625 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(18)
_refine_ls_extinction_coef       0.013(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.981
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3432
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      0.981
_refine_ls_R_factor_all          0.1018
_refine_ls_R_factor_gt           0.0619
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1037P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1616
_refine_ls_wR_factor_ref         0.1960
_reflns_Friedel_coverage         0.865
_reflns_Friedel_fraction_full    0.971
_reflns_Friedel_fraction_max     0.943
_reflns_number_gt                2038
_reflns_number_total             3432
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00460_si_003.cif
_cod_data_source_block           vgb350_1_3m
_cod_original_cell_volume        936.59(15)
_cod_database_code               1543154
_chemical_oxdiff_formula         'C20 H18 N O3 Br'
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C9(H9), C13(H13), C14(H14)
2.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C10(H10A,H10B)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C5(H5), C7(H7), C2(H2), C3(H3), C16(H16), C6(H6), C8(H8),
 C18(H18), C17(H17)
;