Diastereodivergent Intermolecular 1,2-Diamination of Unactivated Alkenes Enabled by Iodine Catalysis

Alkenes Enabled by Iodine Catalysis

Communication

Diastereodivergent Intermolecular 1,2-Diamination of Unactivated

Satoshi Minakata,* Hayato Miwa, Kenya Yamamoto, Arata Hirayama, and Sota Okumura

Cite This: J. Am. Chem. Soc. 2021, 143, 4112 −4118

Read Online

ACCESS

Metrics & More

Article Recommendations

sı Supporting Information

ABSTRACT: The stereospeciﬁc, substrate (nitrogen source)-controlled intermolecular anti- and syn-1,2-diaminations of

unactivated alkenes using the same catalysis (an iodine catalyst) is reported. The combined use of the two potential methods

provides access to all of the disastereomeric forms of 1,2-diamines in spite of the availability of E- and Z-alkenes, and the resulting

products can be readily converted into free vicinal diamines.

he 1,2-diamine substructure is a ubiquitous structural

motif that is found in a number of natural products,

with control of the stereochemistry would be highly desirable

in terms of preparing useful compounds with a minimum

number of steps. Of the various starting materials that are

available for the construction of a 1,2-diamine moiety, alkenes

biologically active compounds, ligands for metal-mediated

−8

catalysis, and organocatalysts (Figure 1a). The development

of an eﬃcient methodology for the synthesis of 1,2-diamines

represent ideal substrates. Even though the nitrogen atom is

a ubiquitous atom that is as important as an oxygen atom in

many organic molecules, the nitrogen version of a diaster-

eodivergent dihydroxylation of alkenes, that is, the Prevost

and Woodward reactions, remains unexplored. Thus, a

versatile method for the robust 1,2-diamination of alkenes

promises to contribute to a more rapid drug discovery but also

could be utilized in the functionalization of a variety of organic

molecules. The stoichiometric, metal-mediated 1,2-diamina-

14−20

tion of alkenes was developed in the 1970s,

and it has

1,22

been applied to some stereoselective reactions.

The

analogous transition-metal-catalyzed intermolecular 1,2-diami-

nation of alkenes has emerged by overcoming the latent

capability of vicinal diamines to coordinate to a metal

3−36

center.

catalysts from the ﬁnal product would be costly in the synthesis

of pharmaceuticals and electronic devices, Muniz’s and

Johnston’s group, using hypervalent iodine(III), developed

Since the removal of trace amounts of metal

37−40

the metal-free diamination of alkenes,

and the former

group applied this method to a catalytic system in which

styrene derivatives are used as substrates. An alternative

metal-free process, namely, electrochemical diamination

42,43

reactions of alkenes, was also reported,

although the

stereochemical outcome was diﬃcult to control and was

dependent on the stability of the structure of the products.

During our research, the catalytic and enantioselective syn-

diamination of styrene derivatives as the main substrates was

reported by Denmark’s group. The diaminations developed

Received: January 8, 2021

Published: March 12, 2021

Figure 1. (a) Selected useful compounds containing a 1,2-diamino

moiety. (b) Synthetic modes for the synthesis of all of the

diastereomers of 1,2-diamino compounds.

2021 American Chemical Society

J. Am. Chem. Soc. 2021, 143, 4112−4118

112

Journal of the American Chemical Society

depicted in Figure 2 ), the aziridination proceeds through an

Communication

so far, for the most part, have been confronted with several

problematic issues. (i) Transition-metal reagents or catalysts

are required. (ii) The generality of such reactions with respect

to alkenes as carbon resources remains unsatisﬁed. (iii) The

removal of substituents on the nitrogen moieties of the initially

formed products to give free diamines requires multistep

reactions and relatively harsh conditions. (iv) An established

protocol for producing diverse arrays of 1,2-diamines with the

intended stereochemistry remains unexplored. If the complete

stereospeciﬁc anti- and syn-1,2-diaminations of acyclic E- and

Z-alkenes as well as cyclic alkenes could be achieved, it would

permit all possible diastereomers of 1,2-diamines to be

synthesized (Figure 1b).

concomitant use of such a nitrogen source and an iodine

catalyst might result in the syn-diamination of alkenes via the

reactive anti-iodoaminated intermediate B′. Both iodoami-

nated intermediates B and B′ should be stereospeciﬁcally

formed via the formation of a three-membered iodonium

intermediate generated by the transfer of iodine to the alkene

from the N-iodinated reactive species A and A′ via the reaction

of the chloramine salt with the iodine catalyst.

In initial investigations directed at identifying a suitable

nitrogen source, various chloramine salts with diﬀerent charges

on the nitrogen atom were screened for use in the iodine-

catalyzed 1,2-diamination. Among these, N-chloro-N-sodio-o-

nitrobenzenesulfonamide (chloramine-Ns) was found to be a

viable nitrogen source (Table S2). Although chloramine-Ns

can be prepared by the reaction of o-nitrobenzenesulfonamide

(nosylamide) with tert-butyl hypochlorite followed by a

We previously reported on the development of unique

nitrogen transfer reactions for simple organic molecules by

utilizing reactive intermediates containing nitrogen-halogen

5,46

bonds.

Among these, the molecular iodine-catalyzed

treatment with NaOH, the in situ generation of chlor-

aziridination of alkenes with N-chloro-N-sodio-p-toluenesulfo-

amine-Ns using nosylamide and a suitable halogen-containing

oxidant would be a general, useful, and practical method for

the formation of 1,2-diamines. When 4-phenyl-1-butene (1a)

namide (chloramine-T) was found to be a versatile method for

7,48

the construction of aziridines from various alkenes.

Even

though the resulting aziridine rings are highly strained and the

nitrogen source has a certain degree of nucleophilicity, when

chloramine-T was used, only a small amount of the ring-

opened product was obtained. The characteristics of the

strained product and the nucleophilic nitrogen source

prompted us to investigate the direct anti-diamination of

alkenes through reactive aziridine intermediates. A suitable

nitrogen source, such as a chloramine salt, could function both

for aziridination and ring-opening reactions, resulting in the

anti-diamination being achieved. From the mechanistic point

of view (proposed pathways for anti- and syn-diamination are

was treated with nosyl-amide in the presence of I as the

catalyst, tert-BuOCl, and NaOH in acetonitrile at 40 °C for 12

h, the desired diaminated product was not obtained. The use of

N-chlorosuccinimide (NCS) instead of tert-BuOCl gave the

1,2-diaminated compound 3a in 23% yield. Although aqueous

NaOCl and Ca(OCl)₂were not so eﬀective, sodium

hypochlorite pentahydrate (NaOCl·5H O) in the solid

form was found to be the most eﬀective oxidant, which

provided the 1,2-diaminated product 3a in 92% isolated yield

(Table 1). In fact, chloramine-Ns was smoothly formed in 91%

Table 1. Optimization of the Chlorinating Oxidant for the

I₂-Catalyzed 1,2-Diamination from Nosylamide

yield (%)

entry

oxidant

base

3a-aziridine

tert-BuOCl

NCS

NaOCl aq

NaOH

Ca(OCl) aq

NaOCl 5H O

yield under mild conditions by treating the nosylamide with

NaOCl·5H O in acetonitrile (Figure S1), indicating that the

chloramine-Ns is initially generated in situ. An additional

beneﬁt is that a nosyl group on the nitrogen can be readily

detached by Fukuyama’s method to furnish the free diaminated

Figure 2. Proposed catalytic cycle for the anti- and syn-1,2-

diamination reactions.

products.

anti-iodoaminated intermediate B that is generated from a

reactive N-chloro-N-iodo-amide species A and an alkene,

followed by a ring-closure reaction. If a nitrogen source could

be prepared that contains both electron-withdrawing groups to

permit a nitrogen−iodine bond to be easily formed in situ and

with two nitrogen moieties within the molecule, the

This highly practical reaction starting from the commercially

available nosylamide, the appropriate oxidant, and an iodine

catalyst prompted us to survey the scope of the reaction for a

broad range of alkenes. Terminal and cyclic alkenes were

successfully converted into 1,2-diamines under conditions I

(Table 2 (a)). The phenyl group-substituted alkene 1b could

113

J. Am. Chem. Soc. 2021, 143, 4112−4118

Journal of the American Chemical Society

Communication

Table 2. Substrate Scope for the I -Catalyzed anti-1,2-Diamination

Reactions were conducted at a concentration of 0.17 M on a 0.5 mmol scale (alkenes being the limiting reagent, 10 mol % of I catalyst). Yields

are the isolated material after puriﬁcation.

also be converted into 3b without oxidation at the benzylic and

allylic positions. The relatively simple aliphatic terminal alkene

triaminated compounds 3i and 3j. The reaction of various

styrene derivatives also aﬀorded the corresponding adducts

3k−3t in good yields. The complete anti-selective diamination

of ﬁve- and six-membered cyclic alkenes proceeded to give 4a

and 4b. Notably, the use of 1,4-cyclohexadiene (3c) selectively

provided the trans-diaminated product 4c, which is a versatile

synthetic intermediate for the total synthesis of oseltamivir

c as well as derivatives containing bromo and ester groups 1d

and 1e could also be used in the diamination reaction. Primary

alcohols and formyl groups were well-tolerated, giving 3f−3h

in good yields, even in the presence of an oxidant. N-

Vinylpyrrolidone and allylamine could be transformed into the

114

J. Am. Chem. Soc. 2021, 143, 4112−4118

Journal of the American Chemical Society

Communication

Table 3. Substrate Scope for the syn-1,2-Diamination

Reactions were conducted at 0.17 M on a 0.5 mmol scale (with alkenes as the limiting reagent) unless otherwise noted. Yields are the isolated

material after puriﬁcation. I : 30 mol %. I : 20 mol %. Chloramine-BBS: 1.5 equiv.

(

Tamiﬂu) that was developed by Shibasaki’s group. The

framework containing two tert-butoxycarbonyl (Boc) groups,

that is, N,N′-bis(tert-butoxycarbonyl)sulfamide (BBS) (Figure

S2). Although BBS is a known compound and is used as a

stabilizer for anaerobically curable adhesives, its use in organic

synthesis is unknown. Although cyclopentene was treated with

BBS in the presence of NaOCl·5H O and the I catalyst at

room temperature (conditions I), the desired syn-diaminated

product was obtained in only a 17% yield, after 45 h. In fact,

the chloramine-BBS, which is thought to be an active species,

was eﬃciently formed by the reaction of BBS with NaOCl·

conjugated cyclic alkenes 4d and 4e were also diaminated

without any detectable formation of a syn-adduct. When the

reaction of E-4-octene (2f) was performed with 2 equiv of

H NNs under conditions I, no desired diaminated product was

formed, but, rather, trans-2,3-di-n-propylaziridine was ob-

tained. Since the ring opening of the aziridine intermediate

would be hampered by the steric hindrance of the two

substituents, running the reaction at room temperature for 12

h in order to produce the maximum amount of the

intermediate aziridine, followed by heating at 80 °C for an

additional 12 h, was found to be the most useful condition for

the internal alkene diamination (Table 2 (b): conditions II).

With the optimal conditions, the desired diamination leading

to the formation of 4f−4i in good yields with complete anti-

selectivity was achieved. The present diamination also

proceeded stereospeciﬁcally to aﬀord 4j from E and 4k from

Z, even when phenyl-conjugated internal alkenes were used.

Although the diamination of internal alkenes required heating

the reaction at 80 °C, hydroxy and siloxy groups were

tolerated, furnishing 4l−4n in good yields. A trisubstituted

oleﬁn 2o and cis-stilbene (2p) were also applicable to the

reaction, but a bromine catalyst was needed, and a small

amount of diastereomer was formed in the case of the reaction

with cis-stilbene. From the results of the product stereo-

chemistry, the present diamination appears to be a stereo-

speciﬁc reaction.

H O in MeCN, and its structure was conﬁrmed by an X-ray

structural analysis (Figures S3 and S4). Since the reason for the

low yield might be due to the solvent used in the diamination

step, further attempts were made to optimize this aspect

(

Tables S6 and S7). The reaction of cyclopentene with

chloramine-BBS in the presence of the iodine catalyst in Et O

selectively aﬀorded the syn-diaminated product 5a in good

yield, and this reaction could be easily scaled up (Table 3). To

verify the utility of this metal-free and catalytic syn-

diamination, other cyclic as well as acyclic alkenes were

examined. Six- and seven-membered alkenes were converted

into the corresponding syn-adducts 5b and 5q. Indenes and

,2-dihydronaphthalenes were also transformed to 5e and 5r−

t in good yields. Even when the starting alkenes were

heteroaromatic compounds 2u and 2v, N-boc-indoles, the syn-

diamination reacted at the 2- and 3-positions, albeit in

moderate yields. The acyclic alkenes 2f and 2g could be

successfully diaminated in a syn manner with no anti adducts

being formed, even in the case of the aromatic-conjugated

alkene 2j. In addition to the anti diamination, the use of

chloramine-BBS in the iodine-catalyzed diamination was also

found to be a stereospeciﬁc reaction.

The present 1,2-anti-diamination can be used to selectively

produce most of the diastereomers of vicinal diamine

compounds starting from the appropriate geometric isomer

of the alkene. The exception is the preparation of syn-

diaminated compounds from cyclic alkenes. On the basis of the

proposed pathway (Figure 2), we focused on a sulfamide

115

J. Am. Chem. Soc. 2021, 143, 4112−4118

Journal of the American Chemical Society

https://pubs.acs.org/doi/10.1021/jacs.1c00228.

Communication

As a unique feature of the anti-diamination reaction, two

diﬀerent nitrogen units could be installed in a carbon−carbon

double bond in a one-pot reaction. For example, when 1.2

equiv of the E-4-octene (2f) was treated with nosylamide and

NaOCl·5H O in the presence of an I catalyst in MeCN at

sent potential precursors of secondary amine derivatives. The

treatment of 3k with 4 equiv of methyl iodide in the presence

of cesium carbonate gave the dimethylated product 3ka in

excellent yield (Scheme 1b). The present syn-diamination was

also applicable for use in a one-pot process, namely, the in situ

ambient temperature for 12 h, followed by the addition of 1.4

preparation of chloramine-BBS from BBS and NaOCl·5H O in

acetonitrile, followed by the removal of the solvents, followed

by the addition of cyclopentene and the iodine catalyst

successfully gave 5a (Scheme 1c). The two Ns groups of the

equiv of H NBoc and NaOCl·5H O, followed by stirring at 45

°C for 12 h, the Ns and the Boc-substituted diamine 4fa were

produced in 85% yield. Each of the protected groups of the

anti-diaminated product 4e could be readily detached,

potential diaminated product 4fa could be individually

leading to the formation of the free diamine, which was

isolated as the p-toluenesulfonic acid salt 4ea. The sulfonyl and

Boc groups of the syn-diaminated product 5e could then be

easily removed to give 5ea in good yield (Scheme 1d).

In conclusion, we report herein on a synthetic strategy that

permits various 1,2-diamine derivatives to be produced from

unactivated alkenes. The nitrogen sources-controlled stereo-

speciﬁc intermolecular anti- and syn-1,2-diamination was

successfully achieved, which are regarded as catalytic aza-

transformed (Scheme 1a). Nosyl-substituted amines repre-

Scheme 1. Application of the Present 1,2-Diamination and

Transformation of 1,2-Diaminated Products

Prevost-Woodward reactions. The present diamination reac-

tions are green-sustainable, because the byproducts that are

produced in the reactions are only NaCl and/or H O.

ASSOCIATED CONTENT

sı Supporting Information

■

The Supporting Information is available free of charge at

Experimental procedures and spectral data (PDF)

Accession Codes

CCDC 1919391−1919392 contain the supplementary crys-

tallographic data for this paper. These data can be obtained

free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by

emailing data_request@ccdc.cam.ac.uk, or by contacting The

Cambridge Crystallographic Data Centre, 12 Union Road,

Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

AUTHOR INFORMATION

■

Corresponding Author

Satoshi Minakata − Department of Applied Chemistry,

Graduate School of Engineering, Osaka University, Suita,

Osaka 565-0871, Japan; orcid.org/0000-0001-9619-

445X ; Email: minakata@chem.eng.osaka-u.ac.jp

Authors

Hayato Miwa − Department of Applied Chemistry, Graduate

School of Engineering, Osaka University, Suita, Osaka 565-

871, Japan

Kenya Yamamoto − Department of Applied Chemistry,

Graduate School of Engineering, Osaka University, Suita,

Osaka 565-0871, Japan

Arata Hirayama − Department of Applied Chemistry,

Graduate School of Engineering, Osaka University, Suita,

Osaka 565-0871, Japan

Sota Okumura − Department of Applied Chemistry, Graduate

School of Engineering, Osaka University, Suita, Osaka 565-

0871, Japan

Complete contact information is available at:

https://pubs.acs.org/10.1021/jacs.1c00228

Notes

The authors declare no competing ﬁnancial interest.

116

J. Am. Chem. Soc. 2021, 143, 4112−4118

Journal of the American Chemical Society

Communication

20) Fristad, W. E.; Brandvold, T. A.; Peterson, J. R.; Thompson, S.

ACKNOWLEDGMENTS

■

R. Conversion of alkenes to 1,2-diazides and 1,2-diamines. J. Org.

Chem. 1985, 50, 3647−3649.

In memory of Prof. Dr. Kilian Mun

iz (1970−2020). This

project was partially supported by the Nippon Light Metal

Company, Ltd., and a Grant-in-Aid for Science Research from

the Japan Society for the Promotion of Science (Grant No.

JP19H02716). We acknowledge the donation of NaOCl·5H O

from the Nippon Light Metal Company, Ltd.

(

21) Mun

Synlett 2003, 211−214.

(22) Muniz, K.; Nieger, M. Enantioselective catalytic diamination of

alkenes with a bisimidoosmium oxidant. Chem. Commun. 2005,

729−2731.

23) Li, G.; Wei, H.-X.; Kim, S. H.; Carducci, M. D. A new

iz, K.; Nieger, M. A first asymmetric diamination of olefins.

electrophilic diamination reaction of alkenes. Angew. Chem., Int. Ed.

2001, 40, 4277−4280.

REFERENCES

■

2) Viso, A.; de la Pradilla, R. F.; Tortosa, M.; García, A.; Flores, A.

1) Lucet, D.; Le Gall, T.; Mioskowski, C. The chemistry of vicinal

diamines. Angew. Chem., Int. Ed. 1998, 37, 2580−2627.

Update of: α ,β -Diamino acids: biological significance and synthetic

approaches. Chem. Rev. 2011, 111, PR1−PR42.

3) Saibabu Kotti, S. R. S.; Timmons, C.; Li, G. Vicinal diamino

(24) Bar, G. L.J.; Lloyd-Jones, G. C.; Booker-Milburn, K. I. Pd(II)-

catalyzed intermolecular 1,2-diamination of conjugated dienes. J. Am.

Chem. Soc. 2005, 127, 7308−7309.

(25) Zhao, B.; Yuan, W.; Du, H.; Shi, Y. Cu(I)-catalyzed

intermolecular diamination of activated terminal olefins. Org. Lett.

2007, 9, 4943−4945.

(26) Iglesias, A.; Pérez, E. G.; Muniz, K. An intermolecular

functionalization as privileged structural elements in biologically

active compounds and exploitation of their synthetic chemistry.

Chem. Chem. Biol. Drug Des. 2006, 67, 101−114.

palladium-catalyzed diamination of unactivated alkenes. Angew.

Chem., Int. Ed. 2010, 49, 8109 −8111.

4) Fujii, A.; Hashiguchi, S.; Uematsu, N.; Ikariya, T.; Noyori, R.

(27) Martínez, C.; Muniz, K. Palladium-catalyzed vicinal difunction-

Ruthenium(II)-catalyzed asymmetric transfer hydrogenation of

ketones using a formic acid-triethylamine mixture. J. Am. Chem. Soc.

alization of internal alkenes: diastereoselective synthesis of diamines.

Angew. Chem., Int. Ed. 2012, 51, 7031−7034.

5) Zhang, W.; Loebach, J. L.; Wilson, S. R.; Jacobsen, E. N.

996, 118, 2521−2522.

Enantioselective epoxidation of unfunctionalized olefins catalyzed by

salen)manganese complexes. J. Am. Chem. Soc. 1990, 112, 2801−

803.

6) Irie, R.; Noda, K.; Ito, Y.; Matsumoto, N.; Katsuki, T. Catalytic

asymmetric epoxidation of unfunctionalized olefins. Tetrahedron Lett.

990, 31, 7345−7348.

7) Uraguchi, D.; Sakaki, S.; Ooi, T. Chiral tetraaminophosphonium

salt-mediated asymmetric direct Henry reaction. J. Am. Chem. Soc.

007, 129, 12392−12393.

8) Nakayama, K.; Maruoka, K. Complete switch of product

(28) Zhang, H.; Pu, W.; Xiong, T.; Li, Y.; Zhou, X.; Sun, K.; Liu, Q.;

Zhang, Q. Copper-catalyzed intermolecular aminocyanation and

diamination of alkenes. Angew. Chem., Int. Ed. 2013, 52, 2529 −2533.

(29) Olson, D. E.; Su, J. Y.; Roberts, D. A.; Du Bois, J. Vicinal

diamination of alkenes under Rh-catalysis. J. Am. Chem. Soc. 2014,

136, 13506−13509.

(31) Zhang, B.; Studer, A. Copper-catalyzed intermolecular

(30) Zhu, Y.; Cornwall, R. G.; Du, H.; Zhao, B.; Shi, Y. Catalytic

diamination of olefins via N −N bond activation. Acc. Chem. Res. 2014,

47, 3665−3678.

aminoazidation of alkenes. Org. Lett. 2014, 16, 1790 −1793.

(32) Yuan, Y.-A.; Lu, D.-F.; Chen, Y.-R.; Xu, H. Iron-catalyzed direct

diazidation for a broad range of olefins. Angew. Chem., Int. Ed. 2016,

55, 534−538.

(33) Ciesielski, J.; Dequirez, G.; Retailleau, P.; Gandon, V.; Dauban,

P. Rhodium-catalyzed alkene difunctionalization with nitrenes. Chem.

- Eur. J. 2016, 22, 9338−9347.

(34) Fu, N.; Sauer, G. S.; Saha, A.; Loo, A.; Lin, S. Metal-catalyzed

electrochemical diazidation of alkenes. Science 2017 , 357 , 575 −579.

(35) Fu, N.; Sauer, G. S.; Lin, S. A general, electrocatalytic approach

to the synthesis of vicinal diamines. Nat. Protoc. 2018, 13, 1725−

1743.

selectivity in asymmetric direct aldol reaction with two different chiral

organocatalysts from a common chiral source. J. Am. Chem. Soc. 2008,

(

30, 17666−17667.

9) Cardona, F.; Goti, A. Metal-catalysed 1,2-diamination reactions.

Nat. Chem. 2009, 1, 269−275.

10) De Jong, S.; Nosal, D. G.; Wardrop, D. J. Methods for direct

alkene diamination, new & old. Tetrahedron 2012, 68, 4067−4105.

11) Prévost, C. Iodo-silver benzoate and its use in the oxidation of

ethylene derivatives into a-glycols. Compt. Rend. 1933, 196, 1129−

131.

12) Woodward, R. B.; Brutcher, F. V., Jr. cis -Hydroxylation of a

syn thetic steroid intermediate with iodine, silver acetate and wet acetic

acid. J. Am. Chem. Soc. 1958, 80, 209−211.

13) Blakemore, D. C.; Castro, L.; Churcher, I.; Rees, D. C.;

Thomas, A. W.; Wilson, D. M.; Wood, A. Organic synthesis provides

opportunities to transform drug discovery. Nat. Chem. 2018, 10, 383−

(36) Shen, S.-J.; Zhu, C.-L.; Lu, D.-F.; Xu, H. Iron-catalyzed direct

olefin diazidation via peroxyester activation promoted by nitrogen-

based ligands. ACS Catal. 2018, 8, 4473−4482.

(

(37) Röben, C.; Souto, J. A.; González, Y.; Lishchynskyi, A.; Muniz,

K. Enantioselective metal-free diamination of styrenes. Angew. Chem.,

Int. Ed. 2011, 50, 9478−9482.

94.

(38) Souto, J. A.; González, Y.; Iglesias, A.; Zian, D.; Lishchynskyi,

14) Aranda, V. G.; Barluenga, J.; Aznar, F. The addition of aromatic

amines to alkenes in the presence of thallium(III) acetate. Synthesis

974, 1974, 504−505.

15) Sharpless, K. B.; Singer, S. P. 1,2-Diamination of 1,3-dienes by

imido selenium compounds. J. Org. Chem. 1976, 41, 2504 −2506.

16) Chong, A. O.; Oshima, K.; Sharpless, K. B. Synthesis of

A.; Mun

alkenes. Chem. - Asian J. 2012, 7, 1103−1111.

(39) Röben, C.; Souto, J. A.; Escudero-Adán, E. C.; Muniz, K.

iz, K. Iodine (III)-promoted intermolecular diamination of

Oxidative diamination promoted by dinuclear iodine(III) reagents.

Org. Lett. 2013, 15, 1008−1011.

(40) Danneman, M. W.; Hong, K. B.; Johnston, J. N. Oxidative

inter-/intramolecular alkene diamination of hydroxy styrenes with

electron-rich amines. Org. Lett. 2015, 17, 2558−2561.

dioxobis(tert -alkylimido)osmium(VIII) and oxotris(tert -alkylimido)-

osmium(VIII) complexes. Stereospecific vicinal diamination of

olefins. J. Am. Chem. Soc. 1977 , 99 , 3420 −3426.

(41) Muniz, K.; Barreiro, L.; Romero, R. M.; Martínez, C. Catalytic

17) Bäckvall, J.-E. Stereospecific palladium-promoted vicinal

asymmetric diamination of styrenes. J. Am. Chem. Soc. 2017, 139,

4354−4357.

diamination of olefins. Tetrahedron Lett. 1978, 19 , 163 −166.

tetrafluoroboric acid-a new reagent in organic synthesis; a convenient

deamination of olefins. Synthesis 1979, 1979, 962−964.

18) Barluenga, J.; Alonso-Cires, L.; Asensio, G. Mercury(II) oxide/

(42) (a) Siu, J. C.; Parry, J. B.; Lin, S. Aminoxyl-catalyzed

electrochemical diazidation of alkenes mediated by a metastable

charge-transfer complex. J. Am. Chem. Soc. 2019 , 141 , 2825 −2831.

(43) Cai, C.-Y.; Shu, X.-M.; Xu, H.-C. Practical and stereoselective

electrocatalytic 1,2-diamination of alkenes. Nat. Commun. 2019, 10,

4953−4959.

19) Becker, P. N.; White, M. A.; Bergman, R. G. A new method for

,2-diamination of alkenes using cyclopentadienylnitrosylcobalt

dimer/NO/LiAlH . J. Am. Chem. Soc. 1980, 102, 5676−5677.

117

J. Am. Chem. Soc. 2021, 143, 4112−4118

Journal of the American Chemical Society

Communication

45) Minakata, S. Utilization of N-X bonds in the synthesis of N-

44) Tao, Z.; Gilbert, B. B.; Denmark, S. E. Catalytic,

enantioselective syn-diamination of alkenes. J. Am. Chem. Soc. 2019,

41, 19161−19170.

heterocycles. Acc. Chem. Res. 2009, 42, 1172−1182.

46) Takeda, Y.; Okumura, S.; Minakata, S. Oxidative dimerization

of aromatic amines using t BuOI uncer miled conditions: Entry to

unsymmetric aromatic azo compounds. Angew. Chem., Int. Ed. 2012,

47) Ando, T.; Kano, D.; Minakata, S.; Ryu, I.; Komatsu, M. Iodine-

1, 7804−7808.

catalyzed aziridination of alkenes using chloramine-T as a nitrogen

source. Tetrahedron 1998, 54, 13485−13494.

48) Minakata, S.; Kano, D.; Oderaotoshi, Y.; Komatsu, M. Silica −

water reaction media: Its application to the formation and ring

opening of aziridines. Angew. Chem., Int. Ed. 2004 , 43 , 79 −81.

49) Herranz, E.; Sharpless, K. B. Osmium-catalyzed vicinal

oxyamination of olefins by N -chloro-N -metallocarbamate. J. Org.

Chem. 1980, 45, 2710−2713.

(

50) Kirihara, M.; Okada, T.; Sugiyama, Y.; Akiyoshi, M.;

Matsunaga, T.; Kimura, Y. Sodium hypochlorite pentahydrate crystals

NaOCl ·5H O): a convenient and environmentally benign oxidant

for organic synthesis. Org. Process Res. Dev. 2017, 21 , 1925 −1937.

51) Fukuyama, T.; Jow, C.-K.; Cheung, M. 2- and 4-Nitro-

benzenesulfonamides: exceptionally versatile means for preparation of

secondary amines and protection of amines. Tetrahedron Lett. 1995,

52) Fukuta, Y.; Mita, T.; Fukuda, N.; Kanai, M.; Shibasaki, M. De

6, 6373−6374.

novo synthesis of Tamiflu via a catalytic asymmetric ring-opening of

meso-aziridines with TMSN . J. Am. Chem. Soc. 2006, 128, 6312−

53) Wu, J.; Dou, Y.; Guillot, R.; Kouklovsky, C.; Vincent, G.

313.

Electrochemical dearomative 2,3-difunctionalization of indoles. J. Am.

Chem. Soc. 2019, 141, 2832−2837.

54) Makai, S.; Falk, E.; Morandi, B. Direct synthesis of unprotected

-azidoamines from alkenes via an iron-catalyzed difunctionalization

reaction. J. Am. Chem. Soc. 2020, 142, 21548 −21555.

55) Kurosawa, W.; Kan, T.; Fukuyama, T. Preparation of secondary

amines from primary amines via 2-nitrobenzenesulfonamides: N -(4-

methoxybenzyl)-3-phenylpropylamine. Org. Synth. 2002, 79, 186−

90.

118