Highly enantioselective one-pot sequential synthesis of valerolactones and pyrazolones bearing all-carbon quaternary stereocentres.
Xu, Yan-Li; Qin, Zhou-Zhou; Wang, Yu-Xia; Zhao, Peng-Fei; Li, Hong-Feng; Du, Zhi-Hong; Da, Chao-Shan; Organic & biomolecular chemistry 19 (2021) 1610–1615; doi:10.1039/d0ob02489a

data_7157852
_publ_section_title
;
 Highly enantioselective one-pot sequential synthesis of valerolactones
 and pyrazolones bearing all-carbon quaternary stereocentres.
;
_journal_issue                   7
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1610
_journal_page_last               1615
_journal_paper_doi               10.1039/d0ob02489a
_journal_volume                  19
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C25 H23 Cl N2 O3'
_chemical_formula_sum            'C25 H23 Cl N2 O3'
_chemical_formula_weight         434.90
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-05-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-06-22 deposited with the CCDC.	2021-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   7.04410(19)
_cell_length_b                   16.2447(4)
_cell_length_c                   18.7200(5)
_cell_measurement_reflns_used    1999
_cell_measurement_temperature    293.44(10)
_cell_measurement_theta_max      68.7660
_cell_measurement_theta_min      5.4380
_cell_volume                     2142.12(10)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      293.44(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0367
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     97.00 126.00   1.00    1.00    --   54.00  38.00 -90.00   29
  2  \w    110.00 136.00   1.00    1.00    --  108.00  93.00 -28.00   26
  3  \w    139.00 165.00   1.00    1.00    --  108.00 107.00  60.00   26
  4  \w    104.00 162.00   1.00    1.00    --  108.00  38.00 150.00   58
  5  \w     48.00 122.00   1.00    1.00    --   54.00  57.00 150.00   74
  6  \w     48.00 115.00   1.00    1.00    --  108.00-111.00 -90.00   67
  7  \w     57.00 111.00   1.00    1.00    --   54.00-125.00-150.00   54
  8  \w     12.00  51.00   1.00    1.00    --    0.00  57.00-180.00   39
  9  \w    -20.00  17.00   1.00    1.00    --    0.00 -57.00  30.00   37
 10  \w    -57.00 -29.00   1.00    1.00    --    0.00 -57.00  30.00   28
 11  \w     88.00 175.00   1.00    1.00    --  108.00  63.00-150.00   87
 12  \w     40.00 110.00   1.00    1.00    --  108.00-111.00 120.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.2080368000
_diffrn_orient_matrix_UB_12      0.0278815000
_diffrn_orient_matrix_UB_13      0.0076669000
_diffrn_orient_matrix_UB_21      0.0421897000
_diffrn_orient_matrix_UB_22      -0.0314179000
_diffrn_orient_matrix_UB_23      -0.0760989000
_diffrn_orient_matrix_UB_31      -0.0528809000
_diffrn_orient_matrix_UB_32      0.0848722000
_diffrn_orient_matrix_UB_33      -0.0306369000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0228
_diffrn_reflns_av_unetI/netI     0.0436
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            5081
_diffrn_reflns_theta_full        66.56
_diffrn_reflns_theta_max         66.56
_diffrn_reflns_theta_min         3.60
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.823
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68308
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
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    1.349
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             912
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.180
_refine_diff_density_min         -0.172
_refine_diff_density_rms         0.035
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.02(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         3222
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0496
_refine_ls_R_factor_gt           0.0416
_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^)+(0.0464P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0957
_refine_ls_wR_factor_ref         0.1031
_reflns_number_gt                2793
_reflns_number_total             3222
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            d0ob02489a2.cif
_cod_data_source_block           xuyl_0218
_cod_depositor_comments
'Adding full bibliography for 7157851--7157852.cif.'
_cod_original_cell_volume        2142.11(9)
_cod_database_code               7157852
_reflns_odcompleteness_completeness 99.78
_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
 At 1.5 times of:
  All O(H) groups
2.a Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C23(H23A,H23B), C12(H12A,H12B), C13(H13A,H13B), C25(H25A,H25B)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C2(H2), C9(H9), C20(H20), C3(H3A), C6(H6), C22(H22), C21(H21),
  C4(H4), C19(H19), C8(H8)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3)
;
_olex2_date_sample_data_collection 2020-05-20
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.620
_oxdiff_exptl_absorpt_empirical_full_min 0.794