Asymmetric Inverse-Electron-Demand Oxa-Diels-Alder Reaction of Allylic Ketones through Dienamine Catalysis.
Shi, Ming-Lin; Zhan, Gu; Zhou, Su-Lan; Du, Wei; Chen, Ying-Chun; Organic letters 18 (2016) 6480–6483; doi:10.1021/acs.orglett.6b03384

data_1555984
_publ_section_title
;
 Asymmetric Inverse-Electron-Demand Oxa-Diels-Alder Reaction of Allylic
 Ketones through Dienamine Catalysis.
;
_journal_issue                   24
_journal_name_full               'Organic letters'
_journal_page_first              6480
_journal_page_last               6483
_journal_paper_doi               10.1021/acs.orglett.6b03384
_journal_volume                  18
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C28 H24 Br N O2'
_chemical_formula_sum            'C28 H24 Br N O2'
_chemical_formula_weight         486.39
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-15
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8033(3)
_cell_length_b                   12.0109(4)
_cell_length_c                   17.2824(7)
_cell_measurement_reflns_used    5918
_cell_measurement_temperature    293.51(10)
_cell_measurement_theta_max      72.4760
_cell_measurement_theta_min      4.4780
_cell_volume                     2242.52(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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_environment      air
_diffrn_ambient_temperature      293.51(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_details
;
  1 omega    1.00   75.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000  -30.0000 74

  2 omega   20.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   57.0000    0.0000 84

  3 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000  -90.0000 94

  4 omega   42.00  109.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171 -159.0000  -47.0000 67

  5 omega  -35.00   66.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -19.0000 -180.0000 101

  6 omega   38.00   91.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

  7 omega   38.00   91.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -120.0000 53

  8 omega   38.00   91.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 53

  9 omega   38.00   91.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

 10 omega   81.00  176.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  -30.0000 95

 11 omega   39.00  109.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 70

 12 omega   40.00   98.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000    0.0000 58

 13 omega   38.00   91.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -180.0000 53

 14 omega   40.00  135.00   1.0000    2.4500
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -150.0000 95

 15 omega  -31.00   63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -77.0000   60.0000 94

 16 omega   10.00   50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000   60.0000 40

 17 omega   10.00  104.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000  150.0000 94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0345369000
_diffrn_orient_matrix_UB_12      -0.1093450000
_diffrn_orient_matrix_UB_13      0.0413055000
_diffrn_orient_matrix_UB_21      0.0218552000
_diffrn_orient_matrix_UB_22      0.0647996000
_diffrn_orient_matrix_UB_23      0.0757105000
_diffrn_orient_matrix_UB_31      -0.1366060000
_diffrn_orient_matrix_UB_32      -0.0172575000
_diffrn_orient_matrix_UB_33      0.0225440000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0405
_diffrn_reflns_av_unetI/netI     0.0353
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            12512
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.697
_diffrn_reflns_theta_min         4.827
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.696
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51048
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
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CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.441
_exptl_crystal_description       plate
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.893
_refine_diff_density_min         -0.426
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 1632 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.045(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     289
_refine_ls_number_reflns         4362
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0974P)^2^+0.2911P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1339
_refine_ls_wR_factor_ref         0.1376
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_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.959
_reflns_number_gt                4148
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_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ol6b03384_si_002.cif
_cod_data_source_block           3i
_cod_original_cell_volume        2242.53(13)
_cod_database_code               1555984
_reflns_odcompleteness_completeness 99.83
_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:
 C005(H005), C00F(H00F)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00A,H00B), C00L(H00D,H00G), C00N(H00H,H00L), C00T(H00M,H00N)
2.c Aromatic/amide H refined with riding coordinates:
 C007(H007), C00C(H00C), C00E(H00E), C00I(H00I), C00J(H00J), C00K(H00K),
 C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00U(H00U),
 C00V(H00V), C00W(H00W)
;
_shelx_res_checksum              73517
_shelx_hkl_checksum              70271
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-04-15
_olex2_submission_special_instructions 'No special instructions were received'