Chemodivergence in Pd-catalyzed desymmetrization of allenes: enantioselective [4+3] cycloaddition, desymmetric allenylic substitution and enynylation.
Luo, Pengfei; Li, Long; Mao, Xinfang; Sun, Zheng; Wang, Yingcheng; Peng, Fangzhi; Shao, Zhihui; Chemical science 14 (2023) 10812–10823; doi:10.1039/d3sc04581a

data_1569920
_publ_section_title
;
 Chemodivergence in Pd-catalyzed desymmetrization of allenes:
 enantioselective [4+3] cycloaddition, desymmetric allenylic substitution
 and enynylation.
;
_journal_issue                   39
_journal_name_full               'Chemical science'
_journal_page_first              10812
_journal_page_last               10823
_journal_paper_doi               10.1039/d3sc04581a
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C26 H25 N O5 S'
_chemical_formula_sum            'C26 H25 N O5 S'
_chemical_formula_weight         463.53
_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     iterative
_audit_creation_date             2022-12-06
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-25 deposited with the CCDC.	2023-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.04550(10)
_cell_length_b                   15.2328(3)
_cell_length_c                   25.3404(5)
_cell_measurement_reflns_used    8055
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      68.354
_cell_measurement_theta_min      3.385
_cell_volume                     2333.59(8)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0586
_diffrn_reflns_av_unetI/netI     0.0437
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            23877
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.410
_diffrn_reflns_theta_min         3.385
_diffrn_source_current           1.1
_diffrn_source_power             0.05500000000000001
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.546
_exptl_absorpt_correction_T_max  0.5849
_exptl_absorpt_correction_T_min  0.4571
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1595 before and 0.0771 after correction.
The Ratio of minimum to maximum transmission is 0.7815.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.319
_exptl_crystal_description       block
_exptl_crystal_F_000             976
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 1529 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.024(8)
_refine_ls_extinction_coef       0.0037(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     339
_refine_ls_number_reflns         4285
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0406
_refine_ls_R_factor_gt           0.0366
_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^)+(0.0520P)^2^+0.2165P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0922
_refine_ls_wR_factor_ref         0.0954
_reflns_Friedel_coverage         0.720
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                3906
_reflns_number_total             4285
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04581a2.cif
_cod_data_source_block           cu_20221205_zh_yn_lpf_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_chemical_absolute_configuration' value 'AD' was changed
to 'ad' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1569919--1569921.cif.
;
_cod_database_code               1569920
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.801
_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. Others
 Sof(C25A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(O4A)=Sof(O5A)=1-FVAR(1)
 Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(O4)=Sof(O5)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C24(H24A,H24B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C17(H17), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23)
3.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C26(H26A,H26B,H26C), C26A(H26D,H26E,H26F)
;
_shelx_res_checksum              37963
_olex2_submission_special_instructions 'No special instructions were received'