Mechanistic Insights into the Origin of Stereoselectivity in an Asymmetric Chlorolactonization Catalyzed by (DHQD)<sub>2</sub>PHAL.
Yousefi, Roozbeh; Sarkar, Aritra; Ashtekar, Kumar; Whitehead, Daniel C.; Kakeshpour, Tayeb; Holmes, Daniel; Reed, Paul; Jackson, James E.; Borhan, Babak; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c01830

data_4134604
_publ_section_title
;
 Mechanistic Insights into the Origin of Stereoselectivity in an
 Asymmetric Chlorolactonization Catalyzed by (DHQD)<sub>2</sub>PHAL.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c01830
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety
'2.5(C H Cl3), C48 H56 N6 O4, 2(C7 H5 O2), 0.5(C7 H6 O2)'
_chemical_formula_sum            'C68 H71.5 Cl7.5 N6 O9'
_chemical_formula_weight         1382.68
_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             2018-01-25
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.01.22 svn.r3481 for OlexSys, GUI svn.r5457)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.4811(3)
_cell_length_b                   19.2956(4)
_cell_length_c                   26.5465(5)
_cell_measurement_reflns_used    8033
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      70.73
_cell_measurement_theta_min      2.83
_cell_volume                     6905.4(2)
_computing_cell_refinement       'APEX2 (BRUKER, V2012.10-0, 2012)'
_computing_data_collection       'COSMO (BRUKER, V1.61, 2009)'
_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  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 8.36
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0691
_diffrn_reflns_av_unetI/netI     0.0669
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            39830
_diffrn_reflns_point_group_measured_fraction_full 0.966
_diffrn_reflns_point_group_measured_fraction_max 0.945
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.195
_diffrn_reflns_theta_min         2.831
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.286
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.6204
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0783 before and 0.0631 after correction. The Ratio of minimum to maximum transmission is 0.8232. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       block
_exptl_crystal_F_000             2884
_exptl_crystal_recrystallization_method
'slow evaporation of CDCl3 solution in NMR tube'
_exptl_crystal_size_max          0.465
_exptl_crystal_size_mid          0.314
_exptl_crystal_size_min          0.178
_refine_diff_density_max         0.675
_refine_diff_density_min         -0.396
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 2851 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.055(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     831
_refine_ls_number_reflns         12876
_refine_ls_number_restraints     43
_refine_ls_restrained_S_all      7.220
_refine_ls_R_factor_all          0.1090
_refine_ls_R_factor_gt           0.0713
_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^)+(0.1218P)^2^+0.9059P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1911
_refine_ls_wR_factor_ref         0.2225
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    0.955
_reflns_Friedel_fraction_max     0.929
_reflns_number_gt                8494
_reflns_number_total             12876
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01830_si_002.cif
_cod_data_source_block           melessa_1
_cod_original_formula_sum        'C68 H71.50 Cl7.50 N6 O9'
_cod_database_code               4134604
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.592
_shelx_estimated_absorpt_t_min   0.310
_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, All O(H) groups
2. Restrained distances
 C10S-Cl7S = C10S-Cl9S = C10S-Cl8S_$1
 1.783 with sigma of 0.02
 C7S-C1S
 1.54 with sigma of 0.02
 Cl7S-Cl9S = Cl9S-Cl8S_$1 = Cl8S_$1-Cl7S
 2.946 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Cl7S \\sim Cl8S \\sim Cl9S \\sim C10S: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Cl1S \\sim Cl2S \\sim Cl3S \\sim Cl4S \\sim Cl5S \\sim Cl6S: within 2A with
sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C6S) = Uanis(C3S)
Uanis(C10S) = Uanis(C9S)
Uanis(C2S) = Uanis(C5S)
Uanis(C1S) = Uanis(C25)
Uanis(C7S) = Uanis(C1A)
Uanis(C6S) = Uanis(C2S)
4. Rigid body (RIGU) restrains
 Cl7S, Cl8S, Cl9S, C10S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: O1S(0.5) H1S(0.5) O2S(0.5) C1S(0.5) C2S(0.5) H2S(0.5) C3S(0.5)
 H3S(0.5) C4S(0.5) H4S(0.5) C5S(0.5) H5S(0.5) C6S(0.5) H6S(0.5) C7S(0.5)
 C10S(0.5) H10S(0.5) Cl7S(0.5) Cl8S(0.5) Cl9S(0.5)
6.a Free rotating group:
 C10S(Cl7S,Cl8S,Cl9S)
6.b Ternary CH refined with riding coordinates:
 C8S(H8S), C9S(H9S), N3(H3), N5(H5), C9(H9), C10(H10), C12(H12), C13(H13),
 C29(H29), C30(H30), C32(H32), C33(H33), C10S(H10S)
6.c Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,
 H17B), C31(H31A,H31B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
 C37(H37A,H37B)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3A), C4(H4), C5(H5A), C6(H6), C20(H20), C21(H21), C23(H23), C24(H24),
 C26(H26), C40(H40), C41(H41), C43(H43), C44(H44), C46(H46), C3A(H3AA),
 C4A(H4A), C5A(H5AA), C6A(H6A), C7A(H7A), C3B(H3B), C4B(H4B), C5B(H5B),
 C6B(H6B), C7B(H7B), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S)
6.e Fitted hexagon refined as free rotating group:
 C1S(C2S,C3S,C4S,C5S,C6S)
6.f Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C28(H28A,H28B,H28C), C38(H38A,H38B,H38C), C48(H48A,H48B,
 H48C)
6.g Idealised tetrahedral OH refined as rotating group:
 O1S(H1S)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop with paratone oil'
_olex2_submission_original_sample_id Melissa_1
_olex2_submission_special_instructions 'No special instructions were received'