Diastereo- and Enantioselective Synthesis of Eight-Membered Heterocycles via an Allylation/Ring Expansion Sequence Enabled by Multiple Catalysis
Yang, Wu-Lin; Wang, Yuan-Lin; Li, Wen; Gu, Bu-Ming; Wang, Si-Wen; Luo, Xiaoyan; Tian, Bo-Xue; Deng, Wei-Ping; ACS Catalysis  (2021) 12557–12564; doi:10.1021/acscatal.1c03711

data_4519056
_publ_section_title
;
 Diastereo- and Enantioselective Synthesis of Eight-Membered Heterocycles
 via an Allylation/Ring Expansion Sequence Enabled by Multiple Catalysis
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              12557
_journal_page_last               12564
_journal_paper_doi               10.1021/acscatal.1c03711
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         '3(C21 H21 N O3), C H Cl3'
_chemical_formula_sum            'C64 H64 Cl3 N3 O9'
_chemical_formula_weight         1125.53
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-12-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                77.061(3)
_cell_angle_beta                 87.047(3)
_cell_angle_gamma                72.519(3)
_cell_formula_units_Z            1
_cell_length_a                   8.8520(8)
_cell_length_b                   12.8850(11)
_cell_length_c                   13.9065(12)
_cell_measurement_reflns_used    9594
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      68.09
_cell_measurement_theta_min      5.43
_cell_volume                     1474.3(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200.0
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.971
_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  0.0509
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            46965
_diffrn_reflns_point_group_measured_fraction_full 0.917
_diffrn_reflns_point_group_measured_fraction_max 0.910
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.180
_diffrn_reflns_theta_min         3.261
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.884
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4883
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1360 before and 0.0880 after correction. The Ratio of minimum to maximum transmission is 0.6484. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       plate
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.402
_refine_diff_density_min         -0.690
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details
;
 Flack x determined using 4267 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.122(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     742
_refine_ls_number_reflns         9839
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0489
_refine_ls_R_factor_gt           0.0478
_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^)+(0.0776P)^2^+0.5055P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1286
_refine_ls_wR_factor_ref         0.1301
_reflns_Friedel_coverage         0.876
_reflns_Friedel_fraction_full    0.860
_reflns_Friedel_fraction_max     0.850
_reflns_number_gt                9582
_reflns_number_total             9839
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c03711_si_002.cif
_cod_data_source_block           lw_f31_02_0m_a
_cod_database_code               4519056
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.834
_shelx_estimated_absorpt_t_min   0.602
_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. Restrained distances
 Cl2A-C4 \\sim Cl2-C4 \\sim Cl0A-C4 \\sim Cl1A-C4 \\sim Cl1-C4
 with sigma of 0.02
 Cl1-C4 \\sim Cl2A-C4 \\sim Cl2-C4 \\sim Cl3A-C4 \\sim Cl0A-C4 \\sim Cl1A-C4
 with sigma of 0.02
3. Rigid bond restraints
 Cl1, Cl1A, Cl0A, Cl3A, Cl2A, Cl2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl1A \\sim Cl0A \\sim Cl3A \\sim Cl2A \\sim Cl2: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(Cl0A) \\sim Ueq, Uanis(Cl1A) \\sim Ueq, Uanis(Cl2A) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
5. Others
 Fixed Sof: Cl2(0.65) H4B(0.6) H4A(0.4) Cl0A(0.6) Cl1A(0.25) Cl2A(0.35)
 Cl3A(0.15)
6.a Ternary CH refined with riding coordinates:
 C00J(H00J), C00K(H00K), C00M(H00M), C00O(H00O), C00Y(H00Y), C011(H011),
 C4(H4B), C4(H4A)
6.b Secondary CH2 refined with riding coordinates:
 C010(H01A,H01B), C013(H01E,H01F), C01B(H01C,H01D), C01K(H01U,H01V), C01N(H01K,
 H01L), C01O(H01Y,H)
6.c Aromatic/amide H refined with riding coordinates:
 N00D(H00D), N00E(H00E), N00F(H00F), C00I(H00I), C00S(H00S), C00V(H00V),
 C00W(H00W), C00Z(H00Z), C012(H012), C014(H014), C017(H017), C018(H018),
 C01A(H01Q), C01C(H01G), C01F(H01H), C01G(H01S), C01I(H01I), C01J(H01J),
 C01L(H01X), C01M(H01M), C01P(H01P), C01Q(H01Z), C01R(H01R), C01S(H01),
 C01T(H01T), C01U(H0AA), C01V(H1AA), C01W(H01W), C021(H021), C022(H022)
6.d X=CH2 refined with riding coordinates:
 C01X(H2AA,HA), C01Z(H01N,H01O), C024(H02D,H02E)
6.e Idealised Me refined as rotating group:
 C020(H02A,H02B,H02C), C025(H02F,H02G,H02H), C027(H02I,H02J,H02K)
;
_olex2_submission_special_instructions 'No special instructions were received'