Enantioselective Allylic Alkylation with 4-Alkyl-1,4-dihydro-pyridines Enabled by Photoredox/Palladium Cocatalysis.
Zhang, Hong-Hao; Zhao, Jia-Jia; Yu, Shouyun; Journal of the American Chemical Society 140 (2018) 16914–16919; doi:10.1021/jacs.8b10766

data_4133525
_publ_section_title
;
 Enantioselective Allylic Alkylation with 4-Alkyl-1,4-dihydro-pyridines
 Enabled by Photoredox/Palladium Cocatalysis.
;
_journal_issue                   49
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16914
_journal_page_last               16919
_journal_paper_doi               10.1021/jacs.8b10766
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '2(C19 H21 N O2)'
_chemical_formula_sum            'C38 H42 N2 O4'
_chemical_formula_weight         590.73
_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     dual
_audit_creation_date             2018-09-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.6036(5)
_cell_length_b                   47.197(2)
_cell_length_c                   7.3012(4)
_cell_measurement_reflns_used    9891
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.776
_cell_measurement_theta_min      4.075
_cell_volume                     3309.4(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.01
_diffrn_measured_fraction_theta_full 0.969
_diffrn_measured_fraction_theta_max 0.966
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0676
_diffrn_reflns_av_unetI/netI     0.0685
_diffrn_reflns_Laue_measured_fraction_full 0.969
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       57
_diffrn_reflns_limit_k_min       -57
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -6
_diffrn_reflns_number            18360
_diffrn_reflns_point_group_measured_fraction_full 0.940
_diffrn_reflns_point_group_measured_fraction_max 0.935
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         55.281
_diffrn_reflns_theta_min         4.324
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.389
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.3299
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1764 before and 0.1282 after correction. The Ratio of minimum to maximum transmission is 0.4394. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_description       plate
_exptl_crystal_F_000             1264
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.426
_refine_diff_density_min         -0.475
_refine_diff_density_rms         0.110
_refine_ls_abs_structure_details
;
 Flack x determined using 1471 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.13(19)
_refine_ls_extinction_coef       0.033(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     430
_refine_ls_number_reflns         5949
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.077
_refine_ls_R_factor_all          0.1524
_refine_ls_R_factor_gt           0.1359
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1472P)^2^+10.8570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3285
_refine_ls_wR_factor_ref         0.3440
_reflns_Friedel_coverage         0.678
_reflns_Friedel_fraction_full    0.899
_reflns_Friedel_fraction_max     0.892
_reflns_number_gt                4943
_reflns_number_total             5949
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b10766_si_002.cif
_cod_data_source_block           mjl18459
_cod_original_cell_volume        3309.3(3)
_cod_database_code               4133525
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.992
_shelx_estimated_absorpt_t_min   0.944
_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 C(H,H,H) groups
2. Others
 Fixed Sof: C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5) C11A(0.5) H11A(0.5)
 H11B(0.5) H11C(0.5) C9B(0.5) H9B(0.5) C10B(0.5) H10B(0.5) C11B(0.5) H11D(0.5)
 H11E(0.5) H11F(0.5)
3.a Ternary CH refined with riding coordinates:
 C1(H1B), C1A(H1AA)
3.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C4A(H4AA,H4AB)
3.c Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14),
 C16(H16), C17(H17), N1A(H1A), C2A(H2A), C6A(H6A), C7A(H7A), C13A(H13A),
 C14A(H14A), C16A(H16A), C17A(H17A), C9A(H9A), C10A(H10A), C9B(H9B), C10B(H10B)
3.d X=CH2 refined with riding coordinates:
 C3(H3A,H3B), C3A(H3AA,H3AB)
3.e Idealised Me refined as rotating group:
 C11(H11G,H11H,H11I), C19(H19D,H19E,H19F), C19A(H19A,H19B,H19C), C11A(H11A,
 H11B,H11C), C11B(H11D,H11E,H11F)
;
_shelx_res_checksum              69713
_shelx_hkl_checksum              8405
_olex2_submission_special_instructions 'No special instructions were received'