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. 2014 Dec 16;47(12):3665-78.
doi: 10.1021/ar500344t. Epub 2014 Nov 17.

Catalytic diamination of olefins via N-N bond activation

Yingguang Zhu  1 , Richard G Cornwall, Haifeng Du, Baoguo Zhao, Yian Shi
Affiliations

Catalytic diamination of olefins via N-N bond activation

Yingguang Zhu et al. Acc Chem Res. .

Abstract

CONSPECTUS: Vicinal diamines are important structural motifs present in various biologically and chemically significant molecules. Direct diamination of olefins provides an effective approach to this class of compounds. Unlike well-established oxidation processes such as epoxidation, dihydroxylation, and aminohydroxylation, direct diamination of olefins had remained a long-standing challenge and had been less well developed. In this Account, we summarize our recent studies on Pd(0)- and Cu(I)-catalyzed diaminations of olefins using di-tert-butyldiaziridinone and its related analogues as nitrogen sources via N-N bond activation. A wide variety of imidazolidinones, cyclic sulfamides, indolines, imidazolinones, and cyclic guanidines can be obtained from conjugated dienes and terminal olefins. For conjugated dienes, the diamination proceeds regioselectively at the internal double bond with the Pd(0) catalyst. Mechanistic studies show that the diamination likely involves a four-membered Pd(II) species resulting from the insertion of Pd(0) into the N-N bond of di-tert-butyldiaziridinone. Interestingly, the Cu(I)-catalyzed process occurs regioselectively at either the terminal or internal double bond depending on the reaction conditions via two mechanistically distinct pathways. The Cu(I) catalyst cleaves the N-N bond of di-tert-butyldiaziridinone to form a Cu(II) nitrogen radical and a four-membered Cu(III) species, which are likely in rapid equilibrium. The Cu(II) nitrogen radical and the four-membered Cu(III) species lead to the terminal and internal diamination, respectively. Terminal olefins are effectively C-H diaminated at the allylic and homoallylic carbons with Pd(0) as catalyst and di-tert-butyldiaziridinone as nitrogen source, likely involving a diene intermediate generated in situ from the terminal olefin via formation of a π-allyl Pd complex and subsequent β-hydride elimination. When di-tert-butylthiadiaziridine 1,1-dioxide is used as nitrogen source, cyclic sulfamides are installed at the terminal carbons via a dehydrogenative diamination process. When α-methylstyrenes (lacking homoallylic hydrogens) react with Pd(0) and di-tert-butyldiaziridinone, spirocyclic indolines are formed with generation of four C-N bonds and one spiro quaternary carbon via allylic and aromatic C-H amination. With Cu(I) catalysts, various terminal olefins can be effectively diaminated at the double bonds using di-tert-butyldiaziridinone, di-tert-butylthiadiaziridine 1,1-dioxide, and 1,2-di-tert-butyl-3-(cyanimino)-diaziridine as nitrogen sources, giving a variety of imidazolidinones, cyclic sulfamides, and cyclic guanidines in good yields, respectively. In the case of monosubstituted olefins using di-tert-butyldiaziridinone as nitrogen source, the resulting diamination products (imidazolidinones) are readily dehydrogenated under the reaction conditions, leading to the corresponding imidazolinones in good yields. Esters can also be diaminated to form the corresponding hydantoins with di-tert-butyldiaziridinone in the presence of a Cu(I) catalyst. A radical mechanism is likely to be operating in these Cu(I)-catalyzed reaction processes. Asymmetric processes have also been developed for the Pd(0)- and Cu(I)-catalyzed diamination reactions. Biologically active compounds such as (+)-CP-99,994 and Sch 425078 have been synthesized via the diamination processes. The diamination reactions described herein provide efficient methods to access a wide variety of vicinal diamines from readily available olefins and show great potential for synthetic applications.

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Figures

Figure 1
Figure 1
Selected examples of 1,2-diamine-containing biologically active molecules.
Figure 2
Figure 2
Di-tert-butyldiaziridinone (1) and its related analogues (2 and 3).
Scheme 1
Scheme 1. Diamination of Olefins via N–N Bond Activation
Scheme 2
Scheme 2. Pd(0)-Catalyzed Diamination of Olefins Using 1
Scheme 3
Scheme 3. Proposed Catalytic Cycle for the Diamination of Olefins with 1
Figure 3
Figure 3
1H NMR monitoring of the reaction between di-tert-butyldiaziridinone (1) and Pd(PPh3)4, as well as the subsequent diamination of (E)-1-phenylbutadiene (8a).
Scheme 4
Scheme 4. Diamination of (E)-1,3-Pentadiene with Four-Membered Pd(II) Species 10
Scheme 5
Scheme 5. Asymmetric Diamination of 1,3-Hexadiene with Selected Ligands (L1–L7)
Scheme 6
Scheme 6. Pd(0)-Catalyzed Asymmetric Diamination of Olefins with Diaziridinone 1
Scheme 7
Scheme 7. Transformations of Optically Active Imidazolidinone 9d
Scheme 8
Scheme 8. NHC-Pd(0)-Catalyzed Asymmetric Diamination of Olefins Using 1
Scheme 9
Scheme 9. Pd(0)-Catalyzed Asymmetric Diamination of Olefins Using 2
Scheme 10
Scheme 10. Pd(0)-Catalyzed Asymmetric Allylic and Homoallylic C–H Diamination
Scheme 11
Scheme 11. Proposed Mechanism for the Pd(0)-Catalyzed C–H Diamination
Scheme 12
Scheme 12. Asymmetric Bisdiamination of 1,9-Decadiene (25)
Scheme 13
Scheme 13. Asymmetric Bisdiamination of 1,7-Octadiene (28)
Scheme 14
Scheme 14. Synthesis of (+)-CP-99,994 via Asymmetric C–H Diamination
Scheme 15
Scheme 15. Pd(0)-Catalyzed Dehydrogenative Diamination Using 2
Scheme 16
Scheme 16. Diamination with a Mixture of (E)-1,3-Pentadiene (8b) and 1-Nonene (22b)
Scheme 17
Scheme 17. Proposed Mechanism for Pd(0)-Catalyzed Dehydrogenative Diamination
Scheme 18
Scheme 18. Cyclization of Sulfamide 37a
Scheme 19
Scheme 19. Pd(0)-Catalyzed Sequential Allylic and Aromatic C–H Aminations with 1
Scheme 20
Scheme 20. Proposed Mechanism for the Formation of Spirocyclic Indolines
Scheme 21
Scheme 21. Deuterium-Labeling Experiment
Scheme 22
Scheme 22. Reaction of α-Methylstyrene (40a) with Pallada(II)cycle 51
Scheme 23
Scheme 23. Heck Reaction/C–H Activation/Amination Sequence with 1
Scheme 24
Scheme 24. Cu(I)-Catalyzed Terminal Diamination of Dienes and Triene Using 1
Scheme 25
Scheme 25. Cu(I)-Catalyzed Asymmetric Terminal Diamination of Dienes and Triene
Scheme 26
Scheme 26. Cu(I)-Catalyzed Asymmetric Terminal Diamination of Dienes and Triene
Scheme 27
Scheme 27. CuBr-Catalyzed Internal Diamination of Conjugated Dienes Using 1
Scheme 28
Scheme 28. Gram-Scale Synthesis of Optically Active Diamine 55
Scheme 29
Scheme 29. Two Distinct Pathways for the Cu(I)-Catalyzed Regioselective Diamination of Conjugated Dienes
Figure 4
Figure 4
Hammett plot with radical substituent constant (σ•) for the terminal diamination of para-substituted (E)-1-phenylbutadienes 8 with CuCl–P(OPh)3 and di-tert-butyldiaziridinone (1).
Scheme 30
Scheme 30. Cu(I)-Catalyzed Regioselective Diamination of Dienes Using 2
Scheme 31
Scheme 31. Cu(I)-Catalyzed Diamination of 1,1-Disubstituted Terminal Olefins
Scheme 32
Scheme 32. Synthesis of Potent NK1 Antagonist Sch 425078
Scheme 33
Scheme 33. Sequential Diamination and Dehydrogenation of Terminal Olefins
Scheme 34
Scheme 34. Deprotection of Imidazolinone 64a
Scheme 35
Scheme 35. Proposed Catalytic Cycle for the Diamination/Dehydrogenation Sequence
Scheme 36
Scheme 36. Cu(I)-Catalyzed Diamination of Terminal Olefins Using 2
Scheme 37
Scheme 37. Cu(I)-Catalyzed Diamination of Olefins Using 3
Scheme 38
Scheme 38. Deprotection of Cyclic Guanidine 72a
Scheme 39
Scheme 39. Cu(I)-Catalyzed Diamination of Esters
Scheme 40
Scheme 40. Deprotection of Hydantoin 75a
Scheme 41
Scheme 41. Proposed Mechanism for Cu(I)-Catalyzed Diamination of Esters
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