Enantioselective Narasaka-Heck cyclizations: synthesis of tetrasubstituted nitrogen-bearing stereocenters.
Race, Nicholas J.; Faulkner, Adele; Fumagalli, Gabriele; Yamauchi, Takayuki; Scott, James S.; Rydén-Landergren, Marie; Sparkes, Hazel A.; Bower, John F.; Chemical science 8 (2017) 1981–1985; doi:10.1039/c6sc04466b

data_1544660
_publ_section_title
;
 Enantioselective Narasaka-Heck cyclizations: synthesis of
 tetrasubstituted nitrogen-bearing stereocenters.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              1981
_journal_page_last               1985
_journal_paper_doi               10.1039/c6sc04466b
_journal_volume                  8
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C42 H40 Cl2 N O P Pd, 3(C H Cl3)'
_chemical_formula_sum            'C45 H43 Cl11 N O P Pd'
_chemical_formula_weight         1141.12
_chemical_name_systematic
;
 ?
;
_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'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2015-04-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-11-24 deposited with the CCDC.
2016-11-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7983(8)
_cell_length_b                   18.7174(11)
_cell_length_c                   19.3028(11)
_cell_measurement_reflns_used    9986
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.74
_cell_measurement_theta_min      2.37
_cell_volume                     4985.3(5)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'Bruker Apex II kappa CCDC area detector'
_diffrn_measurement_device_type  'Bruker Apex II kappa CCDC area detector'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0492
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            44882
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.935
_diffrn_reflns_theta_min         1.515
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.029
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6281
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0897 before and 0.0551 after correction.
The Ratio of minimum to maximum transmission is 0.8424.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       plate
_exptl_crystal_F_000             2304
_exptl_crystal_size_max          0.51
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.699
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.073
_refine_ls_abs_structure_details
;
 Flack x determined using 4410 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   -0.008(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     554
_refine_ls_number_reflns         11959
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0328
_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^)+(0.0266P)^2^+1.4705P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0636
_refine_ls_wR_factor_ref         0.0666
_reflns_Friedel_coverage         0.820
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                10624
_reflns_number_total             11959
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc04466b2.cif
_cod_data_source_block           testo1
_cod_depositor_comments
;Adding full bibliography for 1544660--1544661.cif.

 Adding full bibliography for 1544660--1544661.cif.
;
_cod_database_code               1544660
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl8A-C44 \\sim Cl8-C44 \\sim Cl6A-C44 \\sim Cl6-C44 \\sim Cl7A-C44 \\sim
Cl7-C44
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(Cl7) = Uanis(Cl7A)
Uanis(Cl6) = Uanis(Cl6A)
Uanis(Cl8) = Uanis(Cl8A)
4. Others
 Fixed Sof: Cl6(0.5725) Cl7(0.5725) Cl8(0.5725) H44(0.5725) H44A(0.4275)
 Cl8A(0.4275) Cl7A(0.4275) Cl6A(0.4275)
5.a Ternary CH refined with riding coordinates:
 C7(H7), C44(H44), C44(H44A), C43(H43), C45(H45)
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13),
 C24(H24), C25(H25), C26(H26), C28(H28), C30(H30), C32(H32), C36(H36), C38(H38),
  C40(H40)
5.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C)
;
_shelx_res_checksum              18322
_olex2_submission_special_instructions 'No special instructions were received'