Synthesis of a Polycyclic Halichondrin C1-C14 Fragment via Intermolecular Oxy-Michael/ Trans-Ketalization.
Kim, Dae-Shik; Fang, Francis G.; Choi, Hyeong-Wook; Fang, Hui; The Journal of organic chemistry 84 (2019) 4898–4903; doi:10.1021/acs.joc.8b02404

data_4035931
_publ_section_title
;
 Synthesis of a Polycyclic Halichondrin C1-C14 Fragment via Intermolecular
 Oxy-Michael/ Trans-Ketalization.
;
_journal_issue                   8
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              4898
_journal_page_last               4903
_journal_paper_doi               10.1021/acs.joc.8b02404
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H28 O8'
_chemical_formula_sum            'C22 H28 O8'
_chemical_formula_weight         420.44
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-12
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.02.24 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 92.1810(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.1345(5)
_cell_length_b                   5.78770(10)
_cell_length_c                   10.7579(2)
_cell_measurement_reflns_used    5729
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      72.02
_cell_measurement_theta_min      4.11
_cell_volume                     2061.58(6)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      173(2)
_diffrn_detector_area_resol_mean 8.36
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.969
_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  0.0391
_diffrn_reflns_av_unetI/netI     0.0363
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            11841
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.153
_diffrn_reflns_theta_min         4.112
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.859
_exptl_absorpt_correction_T_max  0.9738
_exptl_absorpt_correction_T_min  0.8448
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0674 before and 0.0557 after correction. The Ratio of minimum to maximum transmission is 0.8675. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.355
_exptl_crystal_description       needle
_exptl_crystal_F_000             896
_exptl_crystal_recrystallization_method 'used as received'
_exptl_crystal_size_max          0.441
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.069
_refine_diff_density_max         0.190
_refine_diff_density_min         -0.161
_refine_diff_density_rms         0.034
_refine_ls_abs_structure_details
;
 Flack x determined using 1431 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.00(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     275
_refine_ls_number_reflns         3862
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0416
_refine_ls_R_factor_gt           0.0367
_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^)+(0.0531P)^2^+0.3171P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0909
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.928
_reflns_number_gt                3518
_reflns_number_total             3862
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b02404_si_001.cif
_cod_data_source_block           esr416b
_cod_database_code               4035931
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.703
_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, All O(H) groups
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5A), C6(H6), C7(H7), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B),
 C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C18(H18), C19(H19)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_contact_crystallographer_email  staples@chemistry.msu.com
_contact_crystallographer_name   'Richard Staples'
_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_special_instructions 'No special instructions were received'