Oxophosphonium-Alkyne Cycloaddition Reactions: Reversible Formation of 1,2-Oxaphosphetes and Six-membered Phosphorus Heterocycles.
Löwe, Pawel; Feldt, Milica; Wünsche, Marius A; Wilm, Lukas F. B.; Dielmann, Fabian; Journal of the American Chemical Society 142 (2020) 9818–9826; doi:10.1021/jacs.0c03494

data_4134986
_publ_section_title
;
 Oxophosphonium-Alkyne Cycloaddition Reactions: Reversible Formation of
 1,2-Oxaphosphetes and Six-membered Phosphorus Heterocycles.
;
_journal_issue                   21
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              9818
_journal_page_last               9826
_journal_paper_doi               10.1021/jacs.0c03494
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         'C62 H78 N6 O P, C F3 O3 S'
_chemical_formula_sum            'C63 H78 F3 N6 O4 P S'
_chemical_formula_weight         1103.34
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-12-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                102.299(2)
_cell_angle_beta                 91.505(2)
_cell_angle_gamma                90.837(2)
_cell_formula_units_Z            4
_cell_length_a                   12.2651(7)
_cell_length_b                   21.5126(12)
_cell_length_c                   23.1911(13)
_cell_measurement_reflns_used    9990
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.43
_cell_measurement_theta_min      2.41
_cell_volume                     5975.3(6)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.971
_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  0.0309
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            66815
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.446
_diffrn_reflns_theta_min         1.913
_exptl_absorpt_coefficient_mu    0.142
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.8468
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1227 before and 0.0536 after correction. The Ratio of minimum to maximum transmission is 0.8468. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.226
_exptl_crystal_description       block
_exptl_crystal_F_000             2352
_exptl_crystal_size_max          0.528
_exptl_crystal_size_mid          0.419
_exptl_crystal_size_min          0.362
_refine_diff_density_max         0.929
_refine_diff_density_min         -0.824
_refine_diff_density_rms         0.069
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1524
_refine_ls_number_reflns         23915
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0958
_refine_ls_R_factor_gt           0.0823
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0691P)^2^+13.6714P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1954
_refine_ls_wR_factor_ref         0.2043
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19867
_reflns_number_total             23915
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c03494_si_002.cif
_cod_data_source_block           compound2a
_cod_depositor_comments
'Adding full bibliography for 4134986--4134987.cif.'
_cod_database_code               4134986
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.929
_olex2_refinement_description
;
1. Others
 Fixed Sof: S2(0.8) F4(0.8) F5(0.8) F6(0.8) O6(0.8) O7(0.8) O8(0.8) C126(0.8)
 S2A(0.2) F4A(0.2) F5A(0.2) F6A(0.2) O6A(0.2) O7A(0.2) O8A(0.2) C1A(0.2)
 Fixed Uiso: H0AA(0.106) H0AB(0.106) H0AC(0.106) H1(0.033) H1AA(0.098)
 H1AB(0.098) H1AC(0.098) H4(0.043) H5(0.052) H6(0.051) H7(0.048) H8(0.041)
 H10(0.043) H11(0.044) H14(0.044) H15(0.048) H16(0.047) H18(0.05) H19A(0.073)
 H19B(0.073) H19C(0.073) H20A(0.095) H20B(0.095) H20C(0.095) H21(0.051)
 H22A(0.095) H22B(0.095) H22C(0.095) H23A(0.077) H23B(0.077) H23C(0.077)
 H26(0.053) H27(0.047) H28(0.047) H30(0.045) H31A(0.083) H31B(0.083)
 H31C(0.083) H32A(0.103) H32B(0.103) H32C(0.103) H33(0.054) H34A(0.098)
 H34B(0.098) H34C(0.098) H35A(0.089) H35B(0.089) H35C(0.089) H37(0.035)
 H38(0.035) H41(0.057) H42(0.061) H43(0.052) H45(0.046) H45A(0.046) H46A(0.076)
 H46B(0.076) H46C(0.076) H47A(0.104) H47B(0.104) H47C(0.104) H48(0.05)
 H49A(0.102) H49B(0.102) H49C(0.102) H50A(0.086) H50B(0.086) H50C(0.086)
 H53(0.056) H54(0.064) H55(0.057) H57(0.049) H58A(0.089) H58B(0.089)
 H58C(0.089) H59A(0.115) H59B(0.115) H59C(0.115) H60(0.052) H61A(0.092)
 H61B(0.092) H61C(0.092) H62A(0.08) H62B(0.08) H62C(0.08) H63(0.061) H66(0.112)
 H67(0.155) H68(0.139) H69(0.132) H70(0.105) H72(0.055) H73(0.051) H76(0.047)
 H77(0.052) H78(0.048) H80(0.047) H81A(0.109) H81B(0.109) H81C(0.109)
 H82A(0.073) H82B(0.073) H82C(0.073) H83(0.048) H84A(0.075) H84B(0.075)
 H84C(0.075) H85A(0.073) H85B(0.073) H85C(0.073) H88(0.046) H89(0.047)
 H90(0.047) H92(0.059) H93A(0.323) H93B(0.323) H93C(0.323) H94A(0.112)
 H94B(0.112) H94C(0.112) H95(0.061) H96A(0.103) H96B(0.103) H96C(0.103)
 H97A(0.108) H97B(0.108) H97C(0.108) H99(0.052) H100(0.05) H103(0.048)
 H104(0.054) H105(0.05) H107(0.059) H10A(0.127) H10B(0.127) H10C(0.127)
 H10D(0.088) H10E(0.088) H10F(0.088) H110(0.053) H11A(0.163) H11B(0.163)
 H11C(0.163) H11D(0.202) H11E(0.202) H11F(0.202) H115(0.069) H116(0.084)
 H117(0.085) H119(0.078) H12A(0.141) H12B(0.141) H12C(0.141) H12D(0.106)
 H12E(0.106) H12F(0.106) H122(0.054) H12G(0.087) H12H(0.087) H12I(0.087)
 H12J(0.105) H12K(0.105) H12L(0.105)
 Fixed X: H0AA(-0.0209) H0AB(0.0363) H0AC(0.0468) H1(0.3639) H1AA(0.2225)
 H1AB(0.1428) H1AC(0.0933) H4(0.5333) H5(0.6769) H6(0.7886) H7(0.7563)
 H8(0.613) H10(-0.0027) H11(0.0105) H14(0.359) H15(0.262) H16(0.1048) H18(-
 0.0357) H19A(-0.0945) H19B(-0.1452) H19C(-0.0445) H20A(0.064) H20B(-0.0431)
 H20C(0.0712) H21(0.3116) H22A(0.2921) H22B(0.3293) H22C(0.2087) H23A(0.473)
 H23B(0.4862) H23C(0.466) H26(0.2809) H27(0.2393) H28(0.1309) H30(0.0469) H31A(-
 0.1024) H31B(-0.1371) H31C(-0.0909) H32A(0.1173) H32B(-0.0017) H32C(0.0121)
 H33(0.2022) H34A(0.0999) H34B(0.1949) H34C(0.2069) H35A(0.3886) H35B(0.3691)
 H35C(0.3862) H37(0.5513) H38(0.4111) H41(0.1896) H42(0.0278) H43(0.0056)
 H45(0.2166) H45A(0.2071) H46A(0.0344) H46B(0.0981) H46C(0.1585) H47A(0.0836)
 H47B(0.0668) H47C(-0.0106) H48(0.4271) H49A(0.3758) H49B(0.4948) H49C(0.438)
 H50A(0.3178) H50B(0.4232) H50C(0.3064) H53(0.759) H54(0.7051) H55(0.5565)
 H57(0.3784) H58A(0.4864) H58B(0.3917) H58C(0.5081) H59A(0.3013) H59B(0.2678)
 H59C(0.3606) H60(0.6298) H61A(0.8107) H61B(0.8074) H61C(0.8296) H62A(0.6658)
 H62B(0.6567) H62C(0.5531) H63(0.8713) H66(0.4954) H67(0.4157) H68(0.5286)
 H69(0.7165) H70(0.7962) H72(0.7631) H73(0.5938) H76(0.2943) H77(0.3125)
 H78(0.4774) H80(0.7104) H81A(0.6075) H81B(0.7144) H81C(0.5986) H82A(0.6837)
 H82B(0.7965) H82C(0.7404) H83(0.5087) H84A(0.3022) H84B(0.3645) H84C(0.4163)
 H85A(0.415) H85B(0.3784) H85C(0.3013) H88(0.9887) H89(1.1438) H90(1.1345)
 H92(0.8939) H93A(1.1059) H93B(1.0608) H93C(0.9981) H94A(0.9795) H94B(0.9931)
 H94C(1.0918) H95(0.7178) H96A(0.8397) H96B(0.7106) H96C(0.7917) H97A(0.7737)
 H97B(0.7182) H97C(0.8482) H99(0.8743) H100(0.7738) H103(0.4594) H104(0.5597)
 H105(0.7466) H107(0.899) H10A(0.911) H10B(1.0197) H10C(0.9345) H10D(0.9039)
 H10E(1.0057) H10F(0.8946) H110(0.5757) H11A(0.3795) H11B(0.4175) H11C(0.4792)
 H11D(0.5238) H11E(0.4382) H11F(0.4106) H115(1.0906) H116(1.0048) H117(0.8531)
 H119(0.7524) H12A(0.6801) H12B(0.6447) H12C(0.7675) H12D(0.6471) H12E(0.5746)
 H12F(0.6101) H122(0.9842) H12G(1.04) H12H(1.1246) H12I(1.1538) H12J(1.1869)
 H12K(1.1561) H12L(1.0939)
 Fixed Y: H0AA(0.3668) H0AB(0.3122) H0AC(0.3131) H1(0.3339) H1AA(0.4352)
 H1AB(0.3818) H1AC(0.4447) H4(0.3089) H5(0.2781) H6(0.1958) H7(0.1422)
 H8(0.1722) H10(0.1685) H11(0.0781) H14(-0.011) H15(-0.0287) H16(0.0261)
 H18(0.123) H19A(0.0366) H19B(0.1018) H19C(0.0717) H20A(0.1731) H20B(0.2006)
 H20C(0.2044) H21(0.1122) H22A(-0.0211) H22B(0.0295) H22C(0.0313) H23A(0.0874)
 H23B(0.0768) H23C(0.017) H26(0.313) H27(0.4129) H28(0.4243) H30(0.2989)
 H31A(0.356) H31B(0.3242) H31C(0.281) H32A(0.4069) H32B(0.3953) H32C(0.4314)
 H33(0.1642) H34A(0.1912) H34B(0.1444) H34C(0.2191) H35A(0.2199) H35B(0.1449)
 H35C(0.1896) H37(0.365) H38(0.4459) H41(0.5513) H42(0.5421) H43(0.4666)
 H45(0.3738) H45A(0.351) H46A(0.3224) H46B(0.2852) H46C(0.3028) H47A(0.4434)
 H47B(0.3706) H47C(0.4004) H48(0.4561) H49A(0.5837) H49B(0.554) H49C(0.5649)
 H50A(0.4249) H50B(0.4656) H50C(0.4982) H53(0.2432) H54(0.1398) H55(0.1199)
 H57(0.2407) H58A(0.132) H58B(0.1693) H58C(0.2033) H59A(0.1728) H59B(0.1493)
 H59C(0.1133) H60(0.3838) H61A(0.3552) H61B(0.4123) H61C(0.3414) H62A(0.3471)
 H62B(0.4192) H62C(0.3719) H63(0.157) H66(0.1047) H67(0.0169) H68(-0.0518) H69(-
 0.0397) H70(0.0472) H72(0.3927) H73(0.4271) H76(0.321) H77(0.3908) H78(0.443)
 H80(0.4436) H81A(0.5358) H81B(0.5378) H81C(0.5186) H82A(0.4191) H82B(0.4391)
 H82C(0.3714) H83(0.2768) H84A(0.332) H84B(0.2869) H84C(0.3549) H85A(0.2086)
 H85B(0.1952) H85C(0.2346) H88(0.1863) H89(0.2219) H90(0.3082) H92(0.3972)
 H93A(0.4173) H93B(0.4669) H93C(0.4561) H94A(0.332) H94B(0.4072) H94C(0.3677)
 H95(0.2392) H96A(0.1466) H96B(0.1448) H96C(0.1339) H97A(0.3091) H97B(0.2475)
 H97C(0.2557) H99(0.0814) H100(0.161) H103(0.3272) H104(0.4097) H105(0.4021)
 H107(0.2619) H10A(0.3303) H10B(0.3319) H10C(0.3882) H10D(0.3611) H10E(0.3166)
 H10F(0.2863) H110(0.1857) H11A(0.2546) H11B(0.1983) H11C(0.2661) H11D(0.1604)
 H11E(0.1332) H11F(0.1954) H115(0.1061) H116(0.0166) H117(-0.0257) H119(0.0144)
 H12A(-0.0481) H12B(-0.0683) H12C(-0.078) H12D(0.0993) H12E(0.0365)
 H12F(0.0543) H122(0.2175) H12G(0.1578) H12H(0.2151) H12I(0.1441) H12J(0.1835)
 H12K(0.2535) H12L(0.2216)
 Fixed Z: H0AA(0.7133) H0AB(0.7398) H0AC(0.6714) H1(0.4396) H1AA(0.8002)
 H1AB(0.8156) H1AC(0.7997) H4(0.3706) H5(0.3075) H6(0.3201) H7(0.3954)
 H8(0.4588) H10(0.3562) H11(0.4048) H14(0.499) H15(0.578) H16(0.6056)
 H18(0.5247) H19A(0.5655) H19B(0.5997) H19C(0.6286) H20A(0.6367) H20B(0.6112)
 H20C(0.5802) H21(0.4208) H22A(0.3741) H22B(0.3365) H22C(0.3615) H23A(0.4722)
 H23B(0.4023) H23C(0.432) H26(0.2951) H27(0.3482) H28(0.4309) H30(0.4998)
 H31A(0.4302) H31B(0.4836) H31C(0.4248) H32A(0.5349) H32B(0.5578) H32C(0.5048)
 H33(0.3315) H34A(0.2539) H34B(0.2272) H34C(0.2296) H35A(0.2904) H35B(0.2833)
 H35C(0.3477) H37(0.7363) H38(0.749) H41(0.5959) H42(0.6422) H43(0.6993)
 H45(0.7434) H45A(0.7178) H46A(0.6681) H46B(0.7111) H46C(0.6562) H47A(0.7977)
 H47B(0.8021) H47C(0.7588) H48(0.604) H49A(0.5972) H49B(0.5897) H49C(0.6523)
 H50A(0.5163) H50B(0.5062) H50C(0.5132) H53(0.5565) H54(0.5577) H55(0.6103)
 H57(0.6882) H58A(0.7128) H58B(0.7512) H58C(0.7492) H59A(0.6045) H59B(0.6627)
 H59C(0.6219) H60(0.6365) H61A(0.6525) H61B(0.6181) H61C(0.5829) H62A(0.5132)
 H62B(0.5486) H62C(0.5421) H63(0.9076) H66(0.8958) H67(0.8258) H68(0.7658)
 H69(0.7731) H70(0.8393) H72(0.8266) H73(0.8769) H76(0.9817) H77(1.0723)
 H78(1.1026) H80(1.0113) H81A(1.0451) H81B(1.0866) H81C(1.1086) H82A(1.1267)
 H82B(1.1019) H82C(1.0739) H83(0.8795) H84A(0.8642) H84B(0.8119) H84C(0.843)
 H85A(0.9309) H85B(0.8626) H85C(0.9113) H88(0.7772) H89(0.835) H90(0.9143)
 H92(0.9603) H93A(0.9203) H93B(0.9756) H93C(0.9128) H94A(1.0202) H94B(1.0448)
 H94C(1.0123) H95(0.8065) H96A(0.7286) H96B(0.7367) H96C(0.7887) H97A(0.7474)
 H97B(0.7052) H97C(0.7097) H99(1.1447) H100(1.2134) H103(1.1822) H104(1.2421)
 H105(1.2551) H107(1.1912) H10A(1.1297) H10B(1.1697) H10C(1.1848) H10D(1.2928)
 H10E(1.2729) H10F(1.2903) H110(1.0968) H11A(1.1) H11B(1.048) H11C(1.0601)
 H11D(1.1855) H11E(1.1325) H11F(1.1809) H115(0.9435) H116(0.8906) H117(0.926)
 H119(1.0661) H12A(0.9485) H12B(1.008) H12C(0.9867) H12D(1.0441) H12E(1.0427)
 H12F(0.9822) H122(1.0569) H12G(1.1266) H12H(1.1265) H12I(1.0945) H12J(1.0023)
 H12K(1.0365) H12L(0.9756)
;
_shelx_res_checksum              41531
_shelx_hkl_checksum              6055
_olex2_submission_special_instructions 'No special instructions were received'