Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles
Trimetaphosphate (TriMP, [P₃O9]³⁻) reacts with PyAOP ([(H₈C₄N)₃PON₄C₅H₃][PF₆]) to yield an activated TriMP, [P₃O₉P(NC₄H₈)₃]⁻ (1), incorporating a phosphonium moiety. Anion 1 is isolated as its bis(triphenylphosphine)iminium (PPN) salt in 70% yield and phosphorylates nucleophiles with elimination of...
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| Format: | Article |
| Language: | en_US |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/123690 |
| _version_ | 1811091251825475584 |
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| author | Shepard, Scott M. Cummins, Christopher C |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Shepard, Scott M. Cummins, Christopher C |
| author_sort | Shepard, Scott M. |
| collection | MIT |
| description | Trimetaphosphate (TriMP, [P₃O9]³⁻) reacts with PyAOP ([(H₈C₄N)₃PON₄C₅H₃][PF₆]) to yield an activated TriMP, [P₃O₉P(NC₄H₈)₃]⁻ (1), incorporating a phosphonium moiety. Anion 1 is isolated as its bis(triphenylphosphine)iminium (PPN) salt in 70% yield and phosphorylates nucleophiles with elimination of phosphoramide OP(NC₄H₈)₃. Treatment of 1 with amines HNR¹R² generates [P₃O₈NR¹R²]²⁻(2a: R¹ = R² = Et; 2b: R¹ = H, R² = tBu) in greater than 70% yield as mixed PPN and alkyl ammonium salts. Treatment of 1 with primary alcohols in the presence of a tertiary amine base results in salts of intact TriMP alkyl esters [P₃O₉R]²⁻(3a: R = Me; 3b: R = Et) in greater than 60% isolated yield. Reaction of 1 with [PPN][H₂PO4] provides orthophosphoryl TriMP (4, [P₄O1₂H₂]²⁻) in 40% yield as the PPN salt. Treatment of 1 with Wittig reagent H₂CPPh₃ (4 equiv) provides phosphorus ylide [P₃O₈CHPPh₃]²⁻ (5) in 61% yield as a mixed salt. Ylide 5 reacts with water to provide [P₃O₈Me]²⁻(6) and with aldehydes to give olefins [P₃O₈CHCHR]²⁻ (7a: R = H; 7b: R = 4-C₆H₄Br), products in which one TriMP oxygen is replaced by a phosphonate P–C linkage. Treatment of intact TriMP derivatives 2a, 2b, 3a, and 7a with aqueous tetrabutylammonium hydroxide results in ring opening to linear triphosphate derivatives. X-ray crystal structures are provided for salts of 1, 2a, 3a, and 4. |
| first_indexed | 2024-09-23T14:59:04Z |
| format | Article |
| id | mit-1721.1/123690 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T14:59:04Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1236902022-10-01T23:47:46Z Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles Shepard, Scott M. Cummins, Christopher C Massachusetts Institute of Technology. Department of Chemistry Massachusetts Institute of Technology. Department of Electrical Engineering and Computer Science Christopher C. Cummins Trimetaphosphate (TriMP, [P₃O9]³⁻) reacts with PyAOP ([(H₈C₄N)₃PON₄C₅H₃][PF₆]) to yield an activated TriMP, [P₃O₉P(NC₄H₈)₃]⁻ (1), incorporating a phosphonium moiety. Anion 1 is isolated as its bis(triphenylphosphine)iminium (PPN) salt in 70% yield and phosphorylates nucleophiles with elimination of phosphoramide OP(NC₄H₈)₃. Treatment of 1 with amines HNR¹R² generates [P₃O₈NR¹R²]²⁻(2a: R¹ = R² = Et; 2b: R¹ = H, R² = tBu) in greater than 70% yield as mixed PPN and alkyl ammonium salts. Treatment of 1 with primary alcohols in the presence of a tertiary amine base results in salts of intact TriMP alkyl esters [P₃O₉R]²⁻(3a: R = Me; 3b: R = Et) in greater than 60% isolated yield. Reaction of 1 with [PPN][H₂PO4] provides orthophosphoryl TriMP (4, [P₄O1₂H₂]²⁻) in 40% yield as the PPN salt. Treatment of 1 with Wittig reagent H₂CPPh₃ (4 equiv) provides phosphorus ylide [P₃O₈CHPPh₃]²⁻ (5) in 61% yield as a mixed salt. Ylide 5 reacts with water to provide [P₃O₈Me]²⁻(6) and with aldehydes to give olefins [P₃O₈CHCHR]²⁻ (7a: R = H; 7b: R = 4-C₆H₄Br), products in which one TriMP oxygen is replaced by a phosphonate P–C linkage. Treatment of intact TriMP derivatives 2a, 2b, 3a, and 7a with aqueous tetrabutylammonium hydroxide results in ring opening to linear triphosphate derivatives. X-ray crystal structures are provided for salts of 1, 2a, 3a, and 4. National Science Foundation (Grant CHE-1305124) 2020-01-28T20:19:38Z 2020-01-28T20:19:38Z 2019-01 2018-11 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 https://hdl.handle.net/1721.1/123690 Shepard, Scott M. and Christopher C. Cummins. "Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles." Journal of the American Chemical Society 141, 5 (January 2019): 1852-1856 © 2019 American Chemical Society en_US http://dx.doi.org/10.1021/jacs.8b12204 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) Prof. Cummins |
| spellingShingle | Shepard, Scott M. Cummins, Christopher C Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles |
| title | Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles |
| title_full | Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles |
| title_fullStr | Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles |
| title_full_unstemmed | Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles |
| title_short | Functionalization of Intact Trimetaphosphate: A Triphosphorylating Reagent for C, N, and O Nucleophiles |
| title_sort | functionalization of intact trimetaphosphate a triphosphorylating reagent for c n and o nucleophiles |
| url | https://hdl.handle.net/1721.1/123690 |
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