Temperature-Controlled Divergent Hydroamination Cyclization [2+2]-Cycloaddition Cascade Reactions of Homopropargylic Amines with 2-Butynedioates: Direct Access To Pyrrolo- b-cyclobutene and Dihydro-1 H-azepines.
Li, Xinhong; Wang, Songmeng; Li, Shengli; Li, Kangming; Mo, Xin; Liu, Lingyan; Chang, Weixing; Li, Jing; The Journal of organic chemistry 84 (2019) 1288–1298; doi:10.1021/acs.joc.8b02730

data_4037550
_publ_section_title
;
 Temperature-Controlled Divergent Hydroamination Cyclization
 [2+2]-Cycloaddition Cascade Reactions of Homopropargylic Amines with
 2-Butynedioates: Direct Access To Pyrrolo- b-cyclobutene and Dihydro-1
 H-azepines.
;
_journal_issue                   3
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              1288
_journal_page_last               1298
_journal_paper_doi               10.1021/acs.joc.8b02730
_journal_volume                  84
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         'C28 H29 N O5'
_chemical_formula_sum            'C28 H29 N O5'
_chemical_formula_weight         459.58
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_symmetry_Int_Tables_number      1
_atom_sites_solution_primary     dual
_audit_creation_date             2018-05-13
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                73.997(14)
_cell_angle_beta                 75.084(14)
_cell_angle_gamma                62.95(2)
_cell_formula_units_Z            1
_cell_length_a                   7.9305(16)
_cell_length_b                   8.0260(16)
_cell_length_c                   10.9367(14)
_cell_measurement_reflns_used    597
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      24.8120
_cell_measurement_theta_min      3.7540
_cell_volume                     588.8(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector_area_resol_mean 16.2116
_diffrn_measured_fraction_theta_full 0.4727
_diffrn_measured_fraction_theta_max 0.4727
_diffrn_measurement_details
;
  1 omega  -41.00   26.00   1.0000    3.0600
omega____ theta____ kappa____ phi______ frames
    -       18.5490  -57.0000 -120.0000 67

  2 omega   66.00   93.00   1.0000    3.0600
omega____ theta____ kappa____ phi______ frames
    -       18.5490  178.0000 -120.0000 27

  3 omega  -52.00   63.00   1.0000    3.0600
omega____ theta____ kappa____ phi______ frames
    -       18.5490  -19.0000  -60.0000 115
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0894474000
_diffrn_orient_matrix_UB_12      0.0244664000
_diffrn_orient_matrix_UB_13      -0.0178189000
_diffrn_orient_matrix_UB_21      0.0407845000
_diffrn_orient_matrix_UB_22      0.0112905000
_diffrn_orient_matrix_UB_23      -0.0659145000
_diffrn_orient_matrix_UB_31      0.0258161000
_diffrn_orient_matrix_UB_32      -0.0972963000
_diffrn_orient_matrix_UB_33      0.0009320000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0298
_diffrn_reflns_av_unetI/netI     0.0701
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            2066
_diffrn_reflns_theta_full        25.0186
_diffrn_reflns_theta_max         25.02
_diffrn_reflns_theta_min         2.90
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51795
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.32 (release 02-08-2013 CrysAlis171 .NET)
(compiled Aug  2 2013,16:46:58)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.2959
_exptl_crystal_description
;
;
_exptl_crystal_F_000             244.1293
_refine_diff_density_max         0.1821
_refine_diff_density_min         -0.2235
_refine_diff_density_rms         0.0425
_refine_ls_abs_structure_details
'Flack, H. D. (1983). Acta Cryst. A39, 876-881.'
_refine_ls_abs_structure_Flack   0(2)
_refine_ls_d_res_high            0.8403
_refine_ls_d_res_low             7.0256
_refine_ls_goodness_of_fit_ref   0.9614
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    51
_refine_ls_number_parameters     309
_refine_ls_number_reflns         1955
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.9614
_refine_ls_R_factor_all          0.0639
_refine_ls_R_factor_gt           0.0573
_refine_ls_shift/su_max          0.6806
_refine_ls_shift/su_mean         0.1330
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1398
_refine_ls_wR_factor_ref         0.1529
_reflns_Friedel_coverage         0.108
_reflns_limit_h_max              6
_reflns_limit_h_min              -9
_reflns_limit_k_max              6
_reflns_limit_k_min              -8
_reflns_limit_l_max              12
_reflns_limit_l_min              -12
_reflns_number_gt                1708
_reflns_number_total             1955
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            jo8b02730_si_004.cif
_cod_data_source_block           A
_cod_depositor_comments
;

2020-10-10
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_sg_symbol_Hall     ' P 1'
_cod_original_formula_moiety     '0.05(C28 H29 N O5)'
_cod_original_formula_sum        'C1.273 H1.318 N0.045 O0.227'
_cod_original_formula_units_Z    22
_cod_original_formula_weight     20.89
_cod_database_code               4037550
_chemical_oxdiff_formula         'C N O'
_reflns_odcompleteness_completeness 72.17
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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:
 C00C(H00C), C00D(H00D), C00L(H00L), C00N(H00N), C00Q(H00Q)
2.b Secondary CH2 refined with riding coordinates:
 C00R(H00a,H00i), C00U(H00u,H00v), C00V(H00w,H00x)
2.c Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H), C00J(H00J),
 C00M(H00M), C00O(H00O), C00P(H00P), C00T(H00T), C00W(H00y), C00X(H00z)
2.d Idealised Me refined as rotating group:
 C00S(H00k,H00r,H00s), C00Y(H00,H,Ha)
;
_olex2_submission_special_instructions 'No special instructions were received'