Palladium-catalyzed asymmetric [4 + 3] cycloaddition of methylene-trimethylenemethane: access to seven-membered exocyclic axially chiral allenes.
Wu, Yafei; Wang, Zhuo; Shan, Yuqian; Ma, Yukun; Li, Teng; Yuan, Chunhao; Guo, Hongchao; Mao, Biming; Chemical science 15 (2024) 9703–9708; doi:10.1039/d4sc01649a

data_1571669
_publ_section_title
;
 Palladium-catalyzed asymmetric [4 + 3] cycloaddition of
 methylene-trimethylenemethane: access to seven-membered exocyclic axially
 chiral allenes.
;
_journal_issue                   25
_journal_name_full               'Chemical science'
_journal_page_first              9703
_journal_page_last               9708
_journal_paper_doi               10.1039/d4sc01649a
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C23 H23 N O3 S'
_chemical_formula_sum            'C23 H23 N O3 S'
_chemical_formula_weight         393.48
_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             2023-10-08
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-25 deposited with the CCDC.	2024-05-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9922(2)
_cell_length_b                   11.1557(2)
_cell_length_c                   16.1415(3)
_cell_measurement_reflns_used    9885
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      74.56
_cell_measurement_theta_min      4.82
_cell_volume                     1979.36(6)
_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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            16934
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         74.600
_diffrn_reflns_theta_min         4.819
_diffrn_source_current           0.95
_diffrn_source_power             0.0475
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.645
_exptl_absorpt_correction_T_max  0.0872
_exptl_absorpt_correction_T_min  0.0109
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1047 before and 0.0591 after correction.
The Ratio of minimum to maximum transmission is 0.1250.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       block
_exptl_crystal_F_000             832
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.632
_refine_diff_density_min         -0.263
_refine_diff_density_rms         0.102
_refine_ls_abs_structure_details
;
 Flack x determined using 1649 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.030(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.133
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     255
_refine_ls_number_reflns         3987
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.133
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0588
_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^)+(0.1052P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1291
_refine_ls_wR_factor_ref         0.1293
_reflns_Friedel_coverage         0.742
_reflns_Friedel_fraction_full    0.982
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                3960
_reflns_number_total             3987
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01649a2.cif
_cod_data_source_block           cu_1008_2_0m
_cod_depositor_comments
'Adding full bibliography for 1571669--1571670.cif.'
_cod_database_code               1571669
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.853
_shelx_estimated_absorpt_t_min   0.734
_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.a Ternary CH refined with riding coordinates:
 C00A(H00A)
2.b Secondary CH2 refined with riding coordinates:
 C00D(H00D,H00E), C00I(H00H,H00I), C00O(H00N,H00O)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00E(H00F), C00G(H00G), C00J(H00J), C00K(H00K),
 C00L(H00L), C00M(H00M), C00Q(H00S), C00R(H00T)
2.d Idealised Me refined as rotating group:
 C00P(H00P,H00Q,H00R), C00S(H00U,H00V,H00W)
;
_shelx_res_checksum              33406
_olex2_submission_special_instructions 'No special instructions were received'