Organocatalysts Fold To Generate an Active Site Pocket for the Mannich Reaction
Neuvonen, Antti J.; Földes, Tamás; Madarász, Ádám; Pápai, Imre; Pihko, Petri M.; ACS Catalysis 7 (2017) 3284–; doi:10.1021/acscatal.7b00336

data_4516730
_publ_section_title
;
 Organocatalysts Fold To Generate an Active Site Pocket for the Mannich
 Reaction
;
_journal_issue                   5
_journal_name_full               'ACS Catalysis'
_journal_page_first              3284
_journal_paper_doi               10.1021/acscatal.7b00336
_journal_volume                  7
_journal_year                    2017
_chemical_absolute_configuration rmad
_chemical_formula_moiety
'C37 H38 F9 N5 O2 S, C0.5 H2 N O0.5, 0.5(C2 N)'
_chemical_formula_sum            'C38.5 H40 F9 N6.5 O2.5 S'
_chemical_formula_weight         836.83
_space_group_crystal_system      orthorhombic
_space_group_IT_number           20
_space_group_name_Hall           'C 2c 2'
_space_group_name_H-M_alt        'C 2 2 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-20
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   13.08003(13)
_cell_length_b                   23.3536(3)
_cell_length_c                   26.5956(3)
_cell_measurement_reflns_used    8510
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      73.8690
_cell_measurement_theta_min      3.7640
_cell_volume                     8124.05(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1977
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_details
;
  1 omega  -48.00   31.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9013   37.0000   30.0000 158

  2 omega -111.00  -15.00   0.5000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -41.9013  -19.0000 -150.0000 192

  3 omega   53.00   99.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -45.0000   90.0000 92

  4 omega   94.00  167.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  125.0000  120.0000 146

  5 omega   59.00  134.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -77.0000    0.0000 150

  6 omega   33.00   91.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  -30.0000    0.0000 116

  7 omega   95.00  166.00   0.5000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      106.6601  125.0000    0.0000 142
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0499296000
_diffrn_orient_matrix_UB_12      0.0596933000
_diffrn_orient_matrix_UB_13      0.0024276000
_diffrn_orient_matrix_UB_21      -0.0140038000
_diffrn_orient_matrix_UB_22      0.0006207000
_diffrn_orient_matrix_UB_23      0.0574952000
_diffrn_orient_matrix_UB_31      0.1057628000
_diffrn_orient_matrix_UB_32      -0.0280948000
_diffrn_orient_matrix_UB_33      0.0064808000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0209
_diffrn_reflns_av_unetI/netI     0.0310
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            12654
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.074
_diffrn_reflns_theta_min         3.786
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.460
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91449
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.368
_exptl_crystal_description
;
;
_exptl_crystal_F_000             3468
_refine_diff_density_max         0.586
_refine_diff_density_min         -0.278
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
;
 Flack x determined using 3259 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.002(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     577
_refine_ls_number_reflns         7833
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0396
_refine_ls_R_factor_gt           0.0384
_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^)+(0.0653P)^2^+3.8849P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1060
_refine_ls_wR_factor_ref         0.1074
_reflns_Friedel_coverage         0.781
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                7612
_reflns_number_total             7833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs7b00336_si_003.cif
_cod_data_source_block           ofi-2-065-urea_20140126
_cod_original_cell_volume        8124.07(15)
_cod_original_formula_sum        'C38.50 H40 F9 N6.50 O2.50 S'
_cod_database_code               4516730
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C38 H42 F9 N7 O3 S1'
_reflns_odcompleteness_completeness 99.55
_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, All N(H) groups, All N(H,H) groups
2. Others
 Sof(F19A)=Sof(F25A)=Sof(F40A)=1-FVAR(1)
 Sof(F19)=Sof(F25)=Sof(F40)=FVAR(1)
 Sof(F45A)=Sof(F50A)=Sof(F58A)=1-FVAR(2)
 Sof(F45)=Sof(F50)=Sof(F58)=FVAR(2)
3.a Ternary CH refined with riding coordinates:
 C23(H23), C26(H26), C31(H31), C38(H38)
3.b Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C29(H29A,H29B), C35(H35A,H35B), C39(H39A,H39B), C42(H42A,
 H42B), C43(H43A,H43B), C47(H47A,H47B), C49(H49A,H49B), C52(H52A,H52B),
 C55(H55A,H55B)
3.c Aromatic/amide H refined with riding coordinates:
 N4(H4), N6(H6), N7(H7), N9(H9), C14(H14), C21(H21), C27(H27), C32(H32),
 C33(H33), C34(H34), C36(H36), C44(H44), C46(H46), C48(H48)
3.d X=CH2 refined with riding coordinates:
 N53(H53A,H53B)
;
_olex2_submission_special_instructions 'No special instructions were received'