Development and Application of α-Heteroatom Ketones in Asymmetric Michael Reaction with β-trans-Nitroalkenes.
Yang, Dongxu; Li, Dan; Wang, Linqing; Zhao, Depeng; Wang, Rui; The Journal of organic chemistry 80 (2015) 4336–4348; doi:10.1021/acs.joc.5b00013

data_4036107
_publ_section_title
;
 Development and Application of \a-Heteroatom Ketones in Asymmetric
 Michael Reaction with \b-trans-Nitroalkenes.
;
_journal_issue                   9
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4336
_journal_page_last               4348
_journal_paper_doi               10.1021/acs.joc.5b00013
_journal_volume                  80
_journal_year                    2015
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C21 H21 N3 O3 S'
_chemical_formula_sum            'C21 H21 N3 O3 S'
_chemical_formula_weight         395.47
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 105.865(7)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   8.5115(6)
_cell_length_b                   11.0465(6)
_cell_length_c                   11.2349(7)
_cell_measurement_reflns_used    1376
_cell_measurement_temperature    294.29(10)
_cell_measurement_theta_max      25.8610
_cell_measurement_theta_min      4.1800
_cell_volume                     1016.09(12)
_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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      294.29(10)
_diffrn_detector_area_resol_mean 16.0733
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
  1 omega  -14.00   21.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -      -16.3571  -99.0000    0.0000 35

  2 omega  -44.00   38.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946  -57.0000 -150.0000 82

  3 omega  -12.00   88.00   1.0000    5.0000
omega____ theta____ kappa____ phi______ frames
    -       19.7946    0.0000   30.0000 100
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0738632000
_diffrn_orient_matrix_UB_12      0.0263430000
_diffrn_orient_matrix_UB_13      -0.0048031000
_diffrn_orient_matrix_UB_21      -0.0274468000
_diffrn_orient_matrix_UB_22      -0.0050871000
_diffrn_orient_matrix_UB_23      -0.0654312000
_diffrn_orient_matrix_UB_31      -0.0358172000
_diffrn_orient_matrix_UB_32      0.0583659000
_diffrn_orient_matrix_UB_33      -0.0034226000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0598
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            4095
_diffrn_reflns_theta_full        25.50
_diffrn_reflns_theta_max         26.00
_diffrn_reflns_theta_min         3.51
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.186
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76016
_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
;
;
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             416
_refine_diff_density_max         0.197
_refine_diff_density_min         -0.183
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.13(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     264
_refine_ls_number_reflns         3301
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0628
_refine_ls_R_factor_gt           0.0493
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0560P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1157
_refine_ls_wR_factor_ref         0.1336
_reflns_number_gt                2680
_reflns_number_total             3301
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5b00013_si_001.cif
_cod_data_source_block           ydx_2
_cod_original_cell_volume        1016.10(11)
_cod_database_code               4036107
_reflns_odcompleteness_completeness 99.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C13) \\sim Ueq, Uanis(C13) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3. Others
 Fixed Sof: H12C(0.5) H12D(0.5) H12A(0.5) H12B(0.5) C13(0.5) H13A(0.5)
 H13B(0.5) H13C(0.5) C13'(0.5) H13D(0.5) H13E(0.5) H13F(0.5)
4.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14)
4.b Secondary CH2 refined with riding coordinates:
 C12(H12C,H12D), C12(H12A,H12B), C15(H15A,H15B)
4.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21)
4.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C13'(H13D,H13E,H13F)
;
_olex2_submission_special_instructions 'No special instructions were received'