Pd-Catalyzed Formal [3 + 3] Heteroannulation of Allylic gem-Diacetates: Synthesis of Chromene-Based Natural Products and Exploration of Photochromic Properties
Kumar, Prashant; Kumar, Pravesh; Venkataramani, Sugumar; Ramasastry, S. S. V.; ACS Catalysis  (2021) 963–970; doi:10.1021/acscatal.1c05450

data_4519239
_publ_section_title
;
 Pd-Catalyzed Formal [3 + 3] Heteroannulation of Allylic gem-Diacetates:
 Synthesis of Chromene-Based Natural Products and Exploration of
 Photochromic Properties
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              963
_journal_page_last               970
_journal_paper_doi               10.1021/acscatal.1c05450
_journal_year                    2021
_chemical_formula_moiety         'C23 H20 N2 O2'
_chemical_formula_sum            'C23 H20 N2 O2'
_chemical_formula_weight         356.427
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-27
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_cell_angle_alpha                97.941(5)
_cell_angle_beta                 98.176(4)
_cell_angle_gamma                110.026(6)
_cell_formula_units_Z            4
_cell_length_a                   11.2619(6)
_cell_length_b                   12.7827(9)
_cell_length_c                   13.9681(8)
_cell_measurement_reflns_used    5553
_cell_measurement_temperature    298
_cell_measurement_theta_max      32.6590
_cell_measurement_theta_min      2.6030
_cell_volume                     1831.9(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.35c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.3 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.9986
_diffrn_measured_fraction_theta_max 0.9388
_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    -69.00 119.00   0.50   20.00    --   29.89  54.00-120.00  376
  2  \w    -69.00 119.00   0.50   20.00    --   29.89  54.00 -90.00  376
  3  \w    -69.00 119.00   0.50   20.00    --   29.89  54.00 120.00  376
  4  \w    -69.00  61.00   0.50   20.00    --   29.89  54.00  60.00  260
  5  \w    -69.00 106.00   0.50   20.00    --   29.89  54.00   0.00  350
;
_diffrn_measurement_device       'two-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Mini (ROW)'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0287793000
_diffrn_orient_matrix_UB_12      0.0396159000
_diffrn_orient_matrix_UB_13      0.0453361000
_diffrn_orient_matrix_UB_21      0.0237627000
_diffrn_orient_matrix_UB_22      0.0439673000
_diffrn_orient_matrix_UB_23      -0.0262010000
_diffrn_orient_matrix_UB_31      -0.0574051000
_diffrn_orient_matrix_UB_32      0.0115003000
_diffrn_orient_matrix_UB_33      -0.0008397000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0563
_diffrn_reflns_av_unetI/netI     0.0654
_diffrn_reflns_Laue_measured_fraction_full 0.9986
_diffrn_reflns_Laue_measured_fraction_max 0.9388
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            38555
_diffrn_reflns_point_group_measured_fraction_full 0.9986
_diffrn_reflns_point_group_measured_fraction_max 0.9388
_diffrn_reflns_theta_full        25.0000
_diffrn_reflns_theta_max         32.76
_diffrn_reflns_theta_min         2.51
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.083
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50934
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.35c (Rigaku Oxford Diffraction, 2017)
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    1.292
_exptl_crystal_description       prism
_exptl_crystal_F_000             752.336
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.9703
_refine_diff_density_min         -0.8903
_refine_diff_density_rms         0.1234
_refine_ls_d_res_high            0.6567
_refine_ls_d_res_low             8.1117
_refine_ls_goodness_of_fit_ref   1.5683
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    68
_refine_ls_number_parameters     493
_refine_ls_number_reflns         12710
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.5683
_refine_ls_R_factor_all          0.1945
_refine_ls_R_factor_gt           0.1148
_refine_ls_shift/su_max          0.0054
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2808
_refine_ls_wR_factor_ref         0.3399
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              18
_reflns_limit_k_min              -19
_reflns_limit_l_max              21
_reflns_limit_l_min              0
_reflns_number_gt                6125
_reflns_number_total             12710
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs1c05450_si_003.cif
_cod_data_source_block           exp_305
_cod_depositor_comments
;

2025-07-30
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C46 H40 N4 O4'
_cod_original_formula_weight         712.855
_cod_original_formula_moiety         '2(C23 H20 N2 O2)'
_cod_original_formula_units_Z            2
_cod_database_code               4519239
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C00V(H00V), C00Q(H00Q), C00X(H00X), C010(H010), C016(H016), C018(H018),
 C00P(H00P), C01C(H01d), C019(H019), C00Z(H00Z), C015(H015), C01A(H01n),
 C01E(H01r), C01I(H01w), C01G(H01v), C00R(H00R), C017(H017), C012(H012),
 C00B(H00B), C00J(H00J), N005(H005), N006(H006)
2.b Idealised Me refined as rotating group:
 C011(H01k,H01l,H01m), C013(H01a,H01b,H01c), C01B(H01o,H01p,H01q), C01D(H01e,
 H01f,H01g), C01F(H01s,H01t,H01u), C01H(H01h,H01i,H01j)
;
_olex2_submission_original_sample_id 'PK spiro'
_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 1.585
_oxdiff_exptl_absorpt_empirical_full_min 0.721