Mechanistic Insights on Orthogonal Selectivity in Heterocycle Synthesis
Maji, Arun; Reddi, Yernaidu; Sunoj, Raghavan B.; Maiti, Debabrata; ACS Catalysis 8 (2018) 10111–; doi:10.1021/acscatal.8b02537

data_4515767
_publ_section_title
;
 Mechanistic Insights on Orthogonal Selectivity in Heterocycle Synthesis
;
_journal_issue                   11
_journal_name_full               'ACS Catalysis'
_journal_page_first              10111
_journal_paper_doi               10.1021/acscatal.8b02537
_journal_volume                  8
_journal_year                    2018
_chemical_formula_moiety         'C16 H16 N2 O2 Pd, C6 H6 O'
_chemical_formula_sum            'C22 H22 N2 O3 Pd'
_chemical_formula_weight         468.81
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-07-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                67.899(7)
_cell_angle_beta                 87.885(6)
_cell_angle_gamma                79.889(6)
_cell_formula_units_Z            2
_cell_length_a                   6.7169(5)
_cell_length_b                   11.3747(7)
_cell_length_c                   13.8249(10)
_cell_measurement_reflns_used    3814
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      30.1910
_cell_measurement_theta_min      2.0200
_cell_volume                     962.96(13)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_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   -110.00  25.00   0.50    8.00    --  -20.00   0.00  36.00  270
  2  \w   -110.00  19.00   0.50    8.00    --  -20.00 -72.00  36.00  258
  3  \w    -69.00   9.00   0.50    8.00    --  -20.00 -72.00-180.00  156
  4  \w    -53.50 -52.50   0.50    8.00    --  -20.00  72.00 -36.00    2
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0660456000
_diffrn_orient_matrix_UB_12      -0.0589637000
_diffrn_orient_matrix_UB_13      0.0077409000
_diffrn_orient_matrix_UB_21      0.0056103000
_diffrn_orient_matrix_UB_22      0.0175386000
_diffrn_orient_matrix_UB_23      -0.0548601000
_diffrn_orient_matrix_UB_31      0.0844061000
_diffrn_orient_matrix_UB_32      0.0297966000
_diffrn_orient_matrix_UB_33      -0.0001591000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0827
_diffrn_reflns_av_unetI/netI     0.1004
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6379
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.009
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.989
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77828
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.617
_exptl_crystal_description       prism
_exptl_crystal_F_000             476
_refine_diff_density_max         0.645
_refine_diff_density_min         -1.112
_refine_diff_density_rms         0.171
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     262
_refine_ls_number_reflns         3328
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0633
_refine_ls_R_factor_gt           0.0472
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0307P)^2^+0.4350P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0892
_refine_ls_wR_factor_ref         0.0994
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2801
_reflns_number_total             3328
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs8b02537_si_002.cif
_cod_data_source_block           dm-amj7-87-1_mo
_cod_original_cell_volume        962.96(12)
_cod_database_code               4515767
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 86.37
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.92
_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, All O(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12), C13(H13),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
2.b Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C)
2.c Idealised tetrahedral OH refined as rotating group:
 O3(H3A)
;
_shelx_res_checksum              61014
_shelx_hkl_checksum              1261
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.308
_oxdiff_exptl_absorpt_empirical_full_min 0.820