Phosphine-catalyzed [4 + 2] annulation of γ-benzyl allenoates: facile synthesis of benzothieno[3,2-b]pyran derivatives.
Ma, Shanshan; Yu, Aimin; Meng, Xiangtai; Organic & biomolecular chemistry 16 (2018) 2885–2892; doi:10.1039/c8ob00004b

data_7156174
_publ_section_title
;
 Phosphine-catalyzed [4 + 2] annulation of \g-benzyl allenoates: facile
 synthesis of benzothieno[3,2-b]pyran derivatives.
;
_journal_issue                   16
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2885
_journal_page_last               2892
_journal_paper_doi               10.1039/c8ob00004b
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C26 H25.12 O5 S'
_chemical_formula_sum            'C26 H25.12 O5 S'
_chemical_formula_weight         449.64
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-12
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2017-12-12 deposited with the CCDC.
2018-03-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.362(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.187(2)
_cell_length_b                   12.8111(15)
_cell_length_c                   19.386(3)
_cell_measurement_reflns_used    2573
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      31.1540
_cell_measurement_theta_min      2.3370
_cell_volume                     4700.3(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.7e (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.7e (Rigaku OD, 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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -75.00 120.00   1.00    8.00    --   30.00  54.00   0.00  195
  2  \w    -31.00  32.00   1.00    8.00    --   30.00  54.00 120.00   63
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0371741000
_diffrn_orient_matrix_UB_12      0.0067343000
_diffrn_orient_matrix_UB_13      -0.0117906000
_diffrn_orient_matrix_UB_21      0.0049048000
_diffrn_orient_matrix_UB_22      0.0493615000
_diffrn_orient_matrix_UB_23      0.0176195000
_diffrn_orient_matrix_UB_31      0.0004736000
_diffrn_orient_matrix_UB_32      0.0241177000
_diffrn_orient_matrix_UB_33      -0.0327705000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0616
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            9363
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.010
_diffrn_reflns_theta_max         25.010
_diffrn_reflns_theta_min         1.920
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.172
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.7e (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.271
_exptl_crystal_description       block
_exptl_crystal_F_000             1897
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.316
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     291
_refine_ls_number_reflns         4152
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0959
_refine_ls_R_factor_gt           0.0587
_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^)+(0.0982P)^2^+0.3570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1527
_refine_ls_wR_factor_ref         0.1989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2806
_reflns_number_total             4152
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob00004b2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7156174--7156175.cif.'
_cod_original_cell_volume        4700.1(10)
_cod_database_code               7156174
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 88.63
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     33.01
_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. Uiso/Uaniso restraints and constraints
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.01
Uanis(C25) = Uanis(C26) = Uanis(C27)
3. Others
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=1-FVAR(1)
 Sof(H25A)=Sof(H25B)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C7(H7)
4.b Secondary CH2 refined with riding coordinates:
 C22(H22A,H22B), C23(H23A,H23B), C2(H2A,H2B), C25(H25A,H25B)
4.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C18(H18), C10(H10), C17(H17), C14(H14), C11(H11), C12(H12), C13(H13)
4.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C1(H1A,H1B,H1C), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              90977
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.539
_oxdiff_exptl_absorpt_empirical_full_min 0.773