Asymmetric α-Photoalkylation of β-Ketocarbonyls by Primary Amine Catalysis: Facile Access to Acyclic All-Carbon Quaternary Stereocenters.
Zhu, Yunbo; Zhang, Long; Luo, Sanzhong; Journal of the American Chemical Society 136 (2014) 14642–14645; doi:10.1021/ja508605a

data_4122644
_publ_section_title
;
 Asymmetric \a-Photoalkylation of \b-Ketocarbonyls by Primary Amine
 Catalysis: Facile Access to Acyclic All-Carbon Quaternary Stereocenters.
;
_journal_issue                   42
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14642
_journal_page_last               14645
_journal_paper_doi               10.1021/ja508605a
_journal_volume                  136
_journal_year                    2014
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H18 Br Cl2 N O3'
_chemical_formula_sum            'C21 H18 Br Cl2 N O3'
_chemical_formula_weight         483.17
_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   mixed
_audit_creation_date             2014-07-10
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.7094(15)
_cell_length_b                   15.687(4)
_cell_length_c                   19.052(4)
_cell_measurement_reflns_used    7414
_cell_measurement_temperature    173.1500
_cell_measurement_theta_max      27.4815
_cell_measurement_theta_min      1.0688
_cell_volume                     2005.2(8)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2013)'
_computing_structure_solution
;
'SHELXS (Sheldrick, 2013)'
;
_diffrn_ambient_temperature      173.1500
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device
;
Saturn724+ (2x2 bin mode)
;
_diffrn_measurement_device_details
;
AFC10: Fixed Chi 2 circle
;
_diffrn_measurement_device_type  'MM007-HF CCD(Saturn 724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_orient_matrix_type       d*Trek
_diffrn_orient_matrix_UB_11      -0.0052
_diffrn_orient_matrix_UB_12      -0.1388
_diffrn_orient_matrix_UB_13      -0.0542
_diffrn_orient_matrix_UB_21      0.0519
_diffrn_orient_matrix_UB_22      0.0118
_diffrn_orient_matrix_UB_23      -0.0351
_diffrn_orient_matrix_UB_31      0.0305
_diffrn_orient_matrix_UB_32      -0.0165
_diffrn_orient_matrix_UB_33      0.0394
_diffrn_radiation_detector       CCD
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0452
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            13270
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.472
_diffrn_reflns_theta_min         2.138
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0000
_diffrn_source_power             1.2000
_diffrn_source_voltage           50.0000
_exptl_absorpt_coefficient_mu    2.339
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.5218
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            Colorless
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.41
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.561
_refine_diff_density_min         -0.238
_refine_diff_density_rms         0.068
_refine_ls_abs_structure_details
;
 Flack x determined using 1748 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.036(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.100
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         4576
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.0346
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0363P)^2^+0.3590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0785
_refine_ls_wR_factor_ref         0.0796
_reflns_Friedel_coverage         0.739
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                4420
_reflns_number_total             4576
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja508605a_si_002.cif
_cod_data_source_block           mx3190
_cod_depositor_comments          'Adding full bibliography for 4122644.cif.'
_cod_original_cell_volume        2005.3(8)
_cod_database_code               4122644
_shelxl_version_number           2013-4
_diffrn_number_total             2660
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B)
2.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C15(H15), C16(H16)
;
_shelx_res_checksum              16104
_shelx_hkl_checksum              1089