The α-Tertiary Amine Motif Drives Remarkable Selectivity for Pd-Catalyzed Carbonylation of β-methylene C–H bonds
Gaunt, Matthew J.; Hogg, Kirsten F.; Trowbridge, Aaron; Álvarez-Pérez, Andrea; Chem. Sci.  (2017) –; doi:10.1039/C7SC03876C

data_1547642
_publ_section_title
;
 The \a-Tertiary Amine Motif Drives Remarkable Selectivity for
 Pd-Catalyzed Carbonylation of \b-methylene C--H bonds
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC03876C
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H28 N2 O5 S'
_chemical_formula_sum            'C20 H28 N2 O5 S'
_chemical_formula_weight         408.50
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_symmetry_space_group_name_Hall  'P -2yac'
_symmetry_space_group_name_H-M   'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2017-08-23 deposited with the CCDC.
2017-10-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.0995(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.2851(2)
_cell_length_b                   16.6804(5)
_cell_length_c                   9.9664(3)
_cell_measurement_reflns_used    5215
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      27.48
_cell_measurement_theta_min      1.00
_cell_volume                     1038.94(6)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor, 1997)'
_computing_data_collection       'COLLECT (Nonius, 1999)'
_computing_data_reduction
'HKL Denzo and Scalepack (Otwinowski & Minor, 1997)'
_computing_molecular_graphics    'Mercury (Macrae et al., 2008)'
_computing_publication_material  SHELXL
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      180(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Nonius KappaCCD'
_diffrn_measurement_method       '\w and \f-scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0416
_diffrn_reflns_av_unetI/netI     0.0502
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            7989
_diffrn_reflns_point_group_measured_fraction_full 0.785
_diffrn_reflns_point_group_measured_fraction_max 0.735
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.486
_diffrn_reflns_theta_min         3.664
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    0.189
_exptl_absorpt_correction_T_max  0.969
_exptl_absorpt_correction_T_min  0.875
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SORTAV (Blessing, 1995)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             436
_exptl_crystal_size_max          0.280
_exptl_crystal_size_mid          0.230
_exptl_crystal_size_min          0.180
_refine_diff_density_max         0.209
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.045
_refine_ls_abs_structure_details
;
Flack x determined using 923 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.04(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     258
_refine_ls_number_reflns         3490
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0552
_refine_ls_R_factor_gt           0.0421
_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^)+(0.0486P)^2^+0.3321P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0972
_refine_ls_wR_factor_ref         0.1051
_reflns_Friedel_coverage         0.480
_reflns_Friedel_fraction_full    0.571
_reflns_Friedel_fraction_max     0.479
_reflns_number_gt                2941
_reflns_number_total             3490
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc03876c2.cif
_cod_data_source_block           mg_k3_0038
_cod_database_code               1547642
_cambridge_user_name             'Kirsten Hogg'
_cambridge_user_crsid            kh566
_cambridge_supervisor_name       'Matthew Gaunt'
_cambridge_supervisor_crsid      mjg32
_cambridge_crystallographer_name 'Andrew Bond'
_cambridge_crystallographer_crsid adb29
_cambridge_sample_id             AA102
_cambridge_data_id               MG_K3_0038
_shelx_estimated_absorpt_t_min   0.949
_shelx_estimated_absorpt_t_max   0.967
_shelx_res_checksum              50422