Phosphine-catalysed α-umpolung addition of nucleophiles to δ-acetoxy allenoates: stereoselective synthesis of 2,4-dienoates.
Hou, Yading; Zhang, Yuwen; Tong, Xiaofeng; Organic & biomolecular chemistry 16 (2018) 5245–5249; doi:10.1039/c8ob00933c

data_7156276
_publ_section_title
;
 Phosphine-catalysed \a-umpolung addition of nucleophiles to \d-acetoxy
 allenoates: stereoselective synthesis of 2,4-dienoates.
;
_journal_issue                   29
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              5245
_journal_page_last               5249
_journal_paper_doi               10.1039/c8ob00933c
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C20 H19 Br O4 S'
_chemical_formula_sum            'C20 H19 Br O4 S'
_chemical_formula_weight         435.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc1zhl9c
_audit_creation_date             2017-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-03-24 deposited with the CCDC.
2018-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                63.5220(10)
_cell_angle_beta                 79.7360(10)
_cell_angle_gamma                89.681(2)
_cell_formula_units_Z            2
_cell_length_a                   7.5123(3)
_cell_length_b                   12.1628(6)
_cell_length_c                   12.1719(4)
_cell_measurement_reflns_used    4510
_cell_measurement_temperature    303(2)
_cell_measurement_theta_max      27.073
_cell_measurement_theta_min      2.77
_cell_volume                     976.11(7)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      303.0
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0301
_diffrn_reflns_av_unetI/netI     0.0489
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13882
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.514
_diffrn_reflns_theta_min         2.765
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.234
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5261
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0695 before and 0.0399 after correction. The Ratio of minimum to maximum transmission is 0.7051. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.481
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.422
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     237
_refine_ls_number_reflns         5858
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0978
_refine_ls_R_factor_gt           0.0427
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0432P)^2^+0.1999P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0926
_refine_ls_wR_factor_ref         0.1121
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3288
_reflns_number_total             5858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob00933c2.cif
_cod_data_source_block           mo_d8v17425_0m
_cod_depositor_comments          'Adding full bibliography for 7156276.cif.'
_cod_database_code               7156276
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.842
_shelx_estimated_absorpt_t_min   0.730
_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 Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C10(H10), C11(H11), C15(H15),
 C16(H16), C18(H18), C19(H19)
2.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              91361
_olex2_submission_special_instructions 'No special instructions were received'