“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_1543155
_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 H17 Br2 N O3'
_chemical_formula_sum            'C20 H17 Br2 N O3'
_chemical_formula_weight         479.17
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_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)
;
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_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.04125(16)
_cell_length_b                   9.8526(4)
_cell_length_c                   31.9892(11)
_cell_measurement_reflns_used    3728
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      72.9140
_cell_measurement_theta_min      4.6860
_cell_volume                     1904.06(11)
_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
;
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)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 8.3200
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details
;
  1 omega  -27.00   68.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       44.1269  -38.0000   90.0000 95

  2 omega   60.00   86.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       44.1269   57.0000   90.0000 26

  3 omega   80.00  114.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       44.1269  126.0000    0.0000 34

  4 omega   36.00   77.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -45.0000 -180.0000 41

  5 omega   31.00   69.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -30.0000 -120.0000 38

  6 omega   41.00   66.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -30.0000  -30.0000 25

  7 omega   30.00   62.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -30.0000 -150.0000 32

  8 omega   68.00   94.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -95.0000  120.0000 26

  9 omega   29.00   55.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -30.0000  -60.0000 26

 10 omega   62.00  108.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -95.0000   30.0000 46

 11 omega   28.00   64.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -95.0000  120.0000 36

 12 omega   34.00   59.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -30.0000  -90.0000 25

 13 omega   64.00  106.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345 -126.0000    0.0000 42

 14 omega   30.00   66.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      102.4345  -30.0000  120.0000 36
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Titan'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0344543000
_diffrn_orient_matrix_UB_12      0.1543741000
_diffrn_orient_matrix_UB_13      -0.0042384000
_diffrn_orient_matrix_UB_21      -0.0434785000
_diffrn_orient_matrix_UB_22      -0.0100241000
_diffrn_orient_matrix_UB_23      -0.0473574000
_diffrn_orient_matrix_UB_31      -0.2488069000
_diffrn_orient_matrix_UB_32      0.0231073000
_diffrn_orient_matrix_UB_33      0.0076512000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0704
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            6780
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.545
_diffrn_reflns_theta_min         2.763
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.566
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36383
_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    1.672
_exptl_crystal_description       needle
_exptl_crystal_F_000             952
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.780
_refine_diff_density_min         -0.784
_refine_diff_density_rms         0.107
_refine_ls_abs_structure_details
;
 Flack x determined using 980 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.09(4)
_refine_ls_extinction_coef       0.0009(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   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     236
_refine_ls_number_reflns         3703
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0766
_refine_ls_R_factor_gt           0.0629
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0675P)^2^+4.9916P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1633
_refine_ls_wR_factor_ref         0.1745
_reflns_Friedel_coverage         0.676
_reflns_Friedel_fraction_full    0.996
_reflns_Friedel_fraction_max     0.936
_reflns_number_gt                3065
_reflns_number_total             3703
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b00460_si_003.cif
_cod_data_source_block           vgb351_1_3s
_cod_original_cell_volume        1904.07(12)
_cod_database_code               1543155
_chemical_oxdiff_formula         'C20 H17 N O3 Br2'
_reflns_odcompleteness_completeness 99.80
_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. Uiso/Uaniso restraints and constraints
C7 \\sim C8 \\sim C9: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C7 \\sim C8 \\sim C9: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.005
Uanis(C8) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C8) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
3.a Ternary CH refined with riding coordinates:
 C8(H8), C7(H7), C9(H9)
3.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C10(H10A,H10B)
3.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C16(H16), C13(H13), C14(H14), C4(H4), C20(H20), C18(H18), C19(H19),
 C2(H2), C3(H3)
;