Phosphine-Catalyzed Enantioselective [2+4] Cycloaddition to Synthesize Pyrrolidin-2-one Fused Dihydropyrans Using α-Substituted Allenoates as C2 Synthons.
Wang, Chang; Jia, Hao; Zhang, Cheng; Gao, Zhenzhen; Zhou, Leijie; Yuan, Chunhao; Xiao, Yumei; Guo, Hongchao; The Journal of organic chemistry 82 (2017) 633–641; doi:10.1021/acs.joc.6b02659

data_4032075
_publ_section_title
;
 Phosphine-Catalyzed Enantioselective [2+4] Cycloaddition to Synthesize
 Pyrrolidin-2-one Fused Dihydropyrans Using \a-Substituted Allenoates as
 C2 Synthons.
;
_journal_issue                   1
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              633
_journal_page_last               641
_journal_paper_doi               10.1021/acs.joc.6b02659
_journal_volume                  82
_journal_year                    2017
_chemical_formula_moiety         'C39 H33 N O4, C H4 O'
_chemical_formula_sum            'C40 H37 N O5'
_chemical_formula_weight         611.70
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-07-14
_audit_creation_method
;
  Olex2 1.1
  (compiled 2011.02.15 svn.r1672, GUI svn.r3494)
;
_cell_angle_alpha                90
_cell_angle_beta                 107.3690(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.9261(2)
_cell_length_b                   12.33670(10)
_cell_length_c                   18.0148(2)
_cell_measurement_reflns_used    13139
_cell_measurement_temperature    108.1
_cell_measurement_theta_max      71.1595
_cell_measurement_theta_min      3.3841
_cell_volume                     3165.97(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'A short history of SHELX (Sheldrick, 2007)'
_diffrn_ambient_temperature      108.1
_diffrn_detector_area_resol_mean 16.0971
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measurement_details
;
  1 omega  -23.00    3.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  111.0000   30.0000 26

  2 omega  -19.00    8.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000   45.0000 -150.0000 27

  3 omega  -67.00  -16.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000  -37.0000 -120.0000 51

  4 omega   26.00   51.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       -8.5000   45.0000 -150.0000 25

  5 omega   50.00   76.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919   37.0000   90.0000 26

  6 omega   19.00  101.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919   64.0000  -14.0000 82

  7 omega   17.00   47.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919  -37.0000 -150.0000 30

  8 omega  -19.00   62.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919  -77.0000  120.0000 81

  9 omega  -29.00   23.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919  -64.0000   29.0000 52

 10 omega   13.00  104.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919   71.0000 -149.0000 91

 11 omega   19.00   44.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919   37.0000   90.0000 25

 12 omega   18.00   87.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919   37.0000  150.0000 69

 13 omega   22.00   68.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       36.7919   37.0000  -30.0000 46

 14 omega   92.00  118.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   60.0000 26

 15 omega  129.00  172.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 43

 16 omega   81.00  107.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   90.0000 26

 17 omega   72.00   98.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  120.0000 26

 18 omega   81.00  175.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000  120.0000 94

 19 omega   40.00  135.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000 -120.0000 95

 20 omega  141.00  170.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 29

 21 omega   95.00  122.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000 -120.0000 27

 22 omega  133.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 45

 23 omega   73.00   99.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000   90.0000 26

 24 omega   53.00   91.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000   30.0000 38

 25 omega   71.00   96.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000 -180.0000 25

 26 omega   75.00  101.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   15.0000  150.0000 26

 27 omega   92.00  168.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  -90.0000 76

 28 omega  136.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 40

 29 omega   92.00  117.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000  120.0000 25

 30 omega  112.00  167.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -90.0000 55

 31 omega   81.00  118.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000   60.0000 37

 32 omega   82.00  172.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   77.0000    0.0000 90

 33 omega   38.00   75.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -15.0000 -180.0000 37

 34 omega   93.00  119.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000   45.0000   90.0000 26

 35 omega  100.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      108.0000  111.0000  -60.0000 76
;
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0571460000
_diffrn_orient_matrix_UB_12      0.0120406000
_diffrn_orient_matrix_UB_13      -0.0580418000
_diffrn_orient_matrix_UB_21      0.0657352000
_diffrn_orient_matrix_UB_22      -0.0919431000
_diffrn_orient_matrix_UB_23      0.0415706000
_diffrn_orient_matrix_UB_31      -0.0640583000
_diffrn_orient_matrix_UB_32      -0.0836554000
_diffrn_orient_matrix_UB_33      -0.0541159000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0392
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            23768
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.970
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.299
_diffrn_reflns_theta_min         3.387
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.671
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93500
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_F_000             1296
_exptl_crystal_size_max          0.340
_exptl_crystal_size_mid          0.300
_exptl_crystal_size_min          0.250
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.296
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 5069 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     835
_refine_ls_number_reflns         11934
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0394
_refine_ls_R_factor_gt           0.0378
_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^)+(0.0577P)^2^+0.4764P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0982
_refine_ls_wR_factor_ref         0.0999
_reflns_Friedel_coverage         0.872
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.951
_reflns_number_gt                11469
_reflns_number_total             11934
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo6b02659_si_002.cif
_cod_data_source_block           exp_4390
_cod_depositor_comments          'Adding full bibliography for 4032075.cif.'
_cod_original_cell_volume        3165.96(6)
_cod_database_code               4032075
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.804
_shelx_hkl_checksum              54651
_shelx_res_checksum              35480
_shelx_shelxl_version_number     2014/7