Access to Substituted Cyclobutenes by Tandem [3,3]-Sigmatropic Rearrangement/[2+2] Cycloaddition of Dipropargylphosphonates under Ag/Co Relay Catalysis
Ni, Qijian; Song, Xiaoxiao; Png, Chin Wen; Zhang, Yongliang; Zhao, Yu; Chemical Science  (2020) –; doi:10.1039/D0SC02972F

data_1559373
_publ_section_title
;
 Access to Substituted Cyclobutenes by Tandem [3,3]-Sigmatropic
 Rearrangement/[2+2] Cycloaddition of Dipropargylphosphonates under Ag/Co
 Relay Catalysis
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02972F
_journal_year                    2020
_chemical_formula_moiety         'C22 H25 O2 P Si'
_chemical_formula_sum            'C22 H25 O2 P Si'
_chemical_formula_weight         380.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-10-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-13 deposited with the CCDC.	2020-10-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.696(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6855(10)
_cell_length_b                   11.4436(9)
_cell_length_c                   15.6122(11)
_cell_measurement_reflns_used    9942
_cell_measurement_temperature    273(2)
_cell_measurement_theta_max      25.278
_cell_measurement_theta_min      3.262
_cell_volume                     2146.8(3)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      273.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1434
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            83096
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.755
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.196
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5437
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1272 before and 0.0886 after correction. The Ratio of minimum to maximum transmission is 0.7292. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.177
_exptl_crystal_description       block
_exptl_crystal_F_000             808
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.463
_refine_diff_density_min         -0.524
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     270
_refine_ls_number_reflns         3773
_refine_ls_number_restraints     617
_refine_ls_restrained_S_all      1.192
_refine_ls_R_factor_all          0.1005
_refine_ls_R_factor_gt           0.0641
_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^)+(0.0822P)^2^+2.3815P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1556
_refine_ls_wR_factor_ref         0.1819
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2556
_reflns_number_total             3773
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02972f2.cif
_cod_data_source_block           1_a
_cod_database_code               1559373
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.958
_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. Restrained distances
 C2-C1
 1.54 with sigma of 0.001
 Si1-C14A \\sim Si1-C14
 with sigma of 0.02
 Si1-C13 \\sim Si1-C13A
 with sigma of 0.02
 Si1-C15A \\sim Si1-C15
 with sigma of 0.02
3. Rigid bond restraints
 C19, C22
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
C5 \\sim C6 \\sim C7 \\sim C2 \\sim C16 \\sim C12 \\sim C17 \\sim C4 \\sim C21
\\sim C1 \\sim C3 \\sim C8 \\sim C19 \\sim C18 \\sim C20 \\sim C11 \\sim C10
\\sim C9 \\sim C22 \\sim C13 \\sim C14 \\sim C15 \\sim C13A \\sim C14A \\sim
C15A: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Si1) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C22) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
5. Rigid body (RIGU) restrains
 Si1, C13, C14, C15, C13A, C14A, C15A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C1(H1A,H1B)
7.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C17(H17), C21(H21), C8(H8), C18(H18), C20(H20), C11(H11), C10(H10),
 C9(H9)
7.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,
 H15C), C13A(H13D,H13E,H13F), C14A(H14D,H14E,H14F), C15A(H15D,H15E,H15F)
;
_shelx_res_checksum              20376
_olex2_submission_special_instructions 'No special instructions were received'