Asymmetric Synthesis of α,β-Unsaturated δ-Lactones through Copper(I)-Catalyzed Direct Vinylogous Aldol Reaction.
Zhang, Hai-Jun; Yin, Liang; Journal of the American Chemical Society 140 (2018) 12270–12279; doi:10.1021/jacs.8b07929

data_4133019
_publ_section_title
;
 Asymmetric Synthesis of \a,\b-Unsaturated \d-Lactones through
 Copper(I)-Catalyzed Direct Vinylogous Aldol Reaction.
;
_journal_issue                   38
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12270
_journal_page_last               12279
_journal_paper_doi               10.1021/jacs.8b07929
_journal_volume                  140
_journal_year                    2018
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C34 H58 O3 Si'
_chemical_formula_sum            'C34 H58 O3 Si'
_chemical_formula_weight         542.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-08-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 97.1420(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.18340(10)
_cell_length_b                   11.0051(2)
_cell_length_c                   21.1383(3)
_cell_measurement_reflns_used    9932
_cell_measurement_temperature    170(2)
_cell_measurement_theta_max      54.89
_cell_measurement_theta_min      3.668
_cell_volume                     1658.10(4)
_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      170.01
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0440
_diffrn_reflns_av_unetI/netI     0.0483
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            18921
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         54.970
_diffrn_reflns_theta_min         3.667
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.544
_exptl_absorpt_correction_T_max  0.7508
_exptl_absorpt_correction_T_min  0.6216
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1131 before and 0.0623 after correction. The Ratio of minimum to maximum transmission is 0.8279. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.087
_exptl_crystal_description       block
_exptl_crystal_F_000             600
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.181
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.037
_refine_ls_abs_structure_details
;
 Flack x determined using 2124 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.030(17)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         6220
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0527
_refine_ls_R_factor_gt           0.0426
_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^)+(0.0371P)^2^+0.2493P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0894
_refine_ls_wR_factor_ref         0.0956
_reflns_Friedel_coverage         0.875
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.974
_reflns_number_gt                5434
_reflns_number_total             6220
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07929_si_001.cif
_cod_data_source_block           mjl18385_0m
_cod_database_code               4133019
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.923
_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:
 C3(H3), C5(H5), C8(H8), C9(H9), C14(H14), C17(H17), C20(H20), C24(H24)
2.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B), C11(H11A,
 H11B), C12(H12A,H12B), C15(H15A,H15B), C16(H16A,H16B), C22(H22A,H22B),
 C23(H23A,H23B), C25(H25A,H25B)
2.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C27(H27)
2.d Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C)
;
_shelx_res_checksum              65872
_shelx_hkl_checksum              22283
_olex2_submission_special_instructions 'No special instructions were received'