Asymmetric Conjugate Addition of Phosphonates to Enones Using Cinchona-Diaminomethylenemalononitrile Organocatalysts.
Arai, Ryoga; Hirashima, Shin-Ichi; Nakano, Tatsuki; Kawada, Masahiro; Akutsu, Hiroshi; Nakashima, Kosuke; Miura, Tsuyoshi; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.9b02553

data_4037891
_publ_section_title
;
 Asymmetric Conjugate Addition of Phosphonates to Enones Using
 Cinchona-Diaminomethylenemalononitrile Organocatalysts.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.9b02553
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H20 N O6 P'
_chemical_formula_sum            'C22 H20 N O6 P'
_chemical_formula_weight         425.36
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-19
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5924)
;
_audit_update_record
;
2019-09-19 # Formatted by publCIF
;
_cell_angle_alpha                90
_cell_angle_beta                 103.485(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.700(3)
_cell_length_b                   6.943(2)
_cell_length_c                   15.369(5)
_cell_measurement_reflns_used    5686
_cell_measurement_temperature    89.95
_cell_measurement_theta_max      26.49
_cell_measurement_theta_min      2.27
_cell_volume                     1006.5(5)
_computing_data_collection       'APEX2 V2014.11-0 (Bruker AXS Inc.,2014)'
_computing_molecular_graphics    'Platon (A.L.Spek, 2003)'
_computing_publication_material
;
pubCIF (Westrip, 2010) and enCIFer (Allen et al. 2004)
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution
'SHELXTL XT Intrinsic Phasing (Sheldrick, 2013)'
_diffrn_ambient_temperature      90
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.333
_diffrn_detector_type            'Bruker APEX II CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'Bruker APEX II Ultra'
_diffrn_radiation_collimation    '0.5 mm  '
_diffrn_radiation_monochromator  'Bruker Helios multilayered confocal mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0220
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            10257
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         26.522
_diffrn_reflns_theta_min         2.159
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Bruker TXS fine-focus Turbo X-ray Source'
_exptl_absorpt_coefficient_mu    0.177
_exptl_absorpt_correction_T_max  0.9955
_exptl_absorpt_correction_T_min  0.9328
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0652 before and 0.0362 after correction. The Ratio of minimum to maximum transmission is 0.9370. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of hesxan and ethyl acetate  by slow evaporation'
_exptl_crystal_size_max          0.289
_exptl_crystal_size_mid          0.286
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.368
_refine_diff_density_min         -0.352
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
 Flack x determined using 1716 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     300
_refine_ls_number_reflns         4120
_refine_ls_number_restraints     451
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.0341
_refine_ls_R_factor_gt           0.0322
_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^)+(0.0383P)^2^+0.5919P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0796
_reflns_Friedel_coverage         0.827
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                3958
_reflns_number_total             4120
_reflns_threshold_expression     'I > 2\s(I)'
_publcif_datablock.id            {b3a48532-8a31-4878-8b8b-627efcbe4e11}
_publcif_info_exptl_table_max_cols 4
_publcif_info_exptl_table_use_headnotes n
_cod_data_source_file            jo9b02553_si_002.cif
_cod_data_source_block           p21
_cod_original_cell_volume        1006.5(6)
_cod_database_code               4037891
_audit_contact_letter
;
 ?
;
_shelx_estimated_absorpt_t_max   0.969
_shelx_estimated_absorpt_t_min   0.951
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.05 and sigma
for terminal atoms of 0.1
3. Others
 Sof(N1A)=Sof(O2A)=Sof(O3A)=1-FVAR(1)
 Sof(O2)=Sof(O3)=Sof(N1)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C1(H1)
4.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
4.c Aromatic/amide H refined with riding coordinates:
 C21(H21), C19(H19), C9(H9), C18(H18), C5(H5), C8(H8), C22(H22), C20(H20),
 C16(H16), C6(H6), C14(H14), C13(H13), C15(H15), C12(H12)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C)
;
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_special_instructions 'No special instructions were received'