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Реакции N-алкил(арил)альд- и кетиминов с эфирами кислот фосфора. Монография

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TBDMSO

P(O)(OR1)2

HNS Tol-p

(SS, 1R, 2S)-(+)-56

3N HCl

P(O)(OR1)2

NH2 (1R, 2S)-(+)-57

6N HCl

P(O)(OH)2

NH2 (1R, 2S)-(-)-58

* 11 1

– N- - (t-Bu- SO), 1 N-n- . * 1 ,

-3

. +- 1 , 3

1 1 1 N-

-1 1 1 N- -

1 1 -

1 2 t-Bu- -

4 (RO)2PHO (SS)-2 1 1 N-

-1 (59) (0 -78°,

LiHMDS, α-1-( -1) (60)

1 1,

(37.6 ÷ 40.4% de), ,

K2CO3 c 37.6 81.8% de [40].

HN S Bu-t

Bu-t

+ (RO)2PHO

P(OR)2

(SS)-59

(Ss, R)-60

, 1

1 1 CH2Cl2 1 K2CO3. +

1 1 N- -

- 1 (61-62). *, - 1 (>95% de), 1 1

(72-86% de). * 1

(63-64) 1 3 1-

1 3 α-1.

K2CO3, CH2Cl2 R2

NHS

(MeO)2PHO

R1 O=P(OMe)2

Ss-61 (R1=H)

(Ss, R)-63 (R1=H)

Ss-62 (R1=Me)

(Ss, R)-64 (R1=Me)

NH2

10N HCl

R1 O=P(OH)2

R2=Ph, 4-MeOC6H4, 4-MeC6H4, 4-ClC6H4, Et, i-Pr, i-Bu, 4-NO2C6H4, n-Bu, t-Bu

+ 6 1, + 1

. ) -

1 ( ) t-Bu 1

KO =P(OMe)2

.. O

S Me(H)

(Rb2CO3), 3 1

, 1 ,

2 1 [41].

O			O	S Bu t		O	S
S							S
S	O			N			N
N	O	Rb2CO3, CH2Cl2		OEt	R		N
N	P CH(OEt)	Rb2CO3, CH2Cl2	R	OEt	R		P
+ H	P CH(OEt)		R	P			P
R	2	1.1.	O	OEt OEt		O	OEt
	OEt						OEt

Bu t

OEt

R = Ph, 4-MeC6H4 ; 4-MeSC6H4; 4-MeOC6H4; 2-FC6H4; 4-FC6H4 ; 4-ClC6H4 ; 4-BrC6H4;

2- , 2- , 3- , 2- , 4 -1, 4 -CNC6H4 ; 4- NO2C6H4

0 in situ 1 (65)

1 1 . -

1 1

[41].

		TolSO3H				R
RCHO + H2NP(O)Ph2		TolSO3H
				Ph2P(O)NHCH
				Ph2P(O)NHCH
		Et2O				SO2Tol-p
						SO2Tol-p
	[Ph P(O) N=CHR]		(EtO)2PHO		(EtO)	P(O)	Ph	EtOH / HCl
	[Ph P(O) N=CHR]				(EtO)	P(O)
2			Na, C6H6		2		NHP(O)Ph2
65			Na, C6H6				NHP(O)Ph2

1. 1.

(EtO)2P(O)CHNH3Cl

+ 1 2 1 1 (66) 1 2-

-Na 2 1 (67)

1 98% 95% 1 1 1 [42]. + 3

(67) 3 (68) 2

2 .

H
Me	Ph				H
Me			Me		H
			Me		Ph
N			H		Ph
		(EtO)2P(O)H (EtO) (O)P		NH
	+ (EtO)2PONa		2
	+ (EtO)2PONa		10oC
OH			OH
66			OH
66			67
			67
1. Pd/C, H2			H
2. Me3SiBr, CHCl3		(HO)2(O)P	NH2
3. MeOH		(HO)2(O)P	NH2
3. MeOH

* 3 1 2-

-Na 1 1 [4] (69 - ) [43]. '-

1 ,

3 1 3 1 (70 - ).

		O
NR	HO	P	NH2
NR		P
		*
	HO
	1.(EtO)2P(O)H, Na
X	2.H2, Pd(C)	X
X		X
Y X Y	3. Me2SiBr	Y X Y
	3. Me2SiBr
	4. MeOH
*		70a (R)
69a R=CH(Ph)CH3(S)		70a (R)
69a R=CH(Ph)CH3(S)
*		70 (S)
69 R=CH(Ph)CH3(R)		70 (S)

" 1 1 1 [4] -

3 [42].

" 1 (71) Na

1:1 1:2 -

1 1- (72) (73) [44].

R1CH=N RN=CHR1 + (R2O)2PHO R2ONa R1CH[P(O)(OR2)2]NH R N=CHR1


71			72
			R2ONa
R1CH=N	R	N=CHR1 + 2(R2O) PHO		R1CH[P(O)(OR2) ]NHRNHCH[P(O)(OR2) ]R1

2			2		2
71			73

$ 2 (74) -

1 1, , N-( - )1 1 (75). *

. 4 K2CO3 Na2CO3 2(1-1) (76)

99%, 92 71%, [45].

O			O
O

			S
S		Na2CO3 Me3C	S
S	R			NH
	R			NH	S OEt
Me3C N	+ (EtO)2PHS
Me3C N	+ (EtO)2PHS	CH2Cl2
	Me	CH2Cl2			P
					P
			Me R		OEt
			Me R
		76, R=Ar, i-Pr, n-Bu, 2-

+ 3 1

- 3 1

1 . % 1 3 1-

2 C=N -1,

[1,7-8].

1.1.2.2 .

+ 1 /,

[1, 7]. ! 1

1, -1

9 1 1. +

3 , 1

3 1.

+ 1 (77) 1 3 -

, (R)-BINOL (78 -

.1) [46-49].

	780	(10 1%)	HN	OMe
RCH N	OMe + (EtO)2PHO

			R	P(O)(OEt)2
77

R=Ph, 2-MeC6H4, 2-NO2C6H4, PhCH=CH, 4-MeC6H4CH=CH, 4-Cl C6H4CH=CH, 2-MeC6H4CH=CH, 2-CIC6H4CH=CH,

2-NO2C6H4Ch=CH, 2-CF3C6H4CH=CH, 1- CH=CH

+ 1 (79) (78 )

72-97%, 2 52-90% .

O O

O H

78, Ar=Ph( ), Ar=4-NO2C6H4( ), Ar=4-CF3C6H4( ), Ar=3,5-(CF3)2C6H3( )

. 1. 7 1 3 BINOL- (78 - )

/ DFT-

1 1 (R)-BINOL -

(78 ) [48, 50].

(80) ( .2), (78 ) :

1 /,

1 /, 1 1

1 re- 1 2.

( 1 1, , (78 ) -

/. ) -

(80).

	CF3
		CF3 H O			OR
O		CF3 H O		P	OR
O	P		O	:
	P		O
			Ar
	CF		Ar
	CF	3	O	H
		3	H	H
			H
			N
F3C			Ar

. 2. ' (80).

5 BINOL- 1 ( =Na, Ca, Mg)

1. , 1 1 2 1 -

Mg- , 2

96-99% [51].

( 2 1-

1 2 1 [52].

RCH=NR1	+ (EtO) PHO	TsCl (0.1 2.)		R1CH		P(O)(OEt)


	2	CH2Cl2, 1.	1.		2
	2				2

NHR2

R1=Ph, 4-MeC6H4, 4-i-PrC6H4, 4-MeOC6H4, 4-NO2C6H4, PhCH=CH, R2=Ph,

3-NO2C6H4,

+ 1 1 1 1

2 1 2 (81)

. 4 1. $1 (82)

(82), 1 ,

(83), 3 1 .

TsOP(OEt)2 + RCH=N+HR1Cl-		R1NHCHRP+(OEt)2OTsCl-
81	82	83
	R1NH-CHRP(O)(OEt)2 + TsCl

!39 1992 2 – 2-

%, 2-

N-1 1 1 [53]. + -

2 2

1 N- 1-

1 [54-55], N-1 2 1

[56].

4 2 1 1 1 (84), 1 3 1 -2 1, -

, N-3 -

(85) [57-58].

(	)			BF3 .Et2O ( )
(	)	n		BF3 .Et2O ( )
			R + (EtO)2PHO		n			P(O)(OEt)2
				( 201 %)				P(O)(OEt)2
				( 201 %)
		N				N		R
84						H	85
						H	85
		R=Me, i -Pr, n- Bu,Ph,4-Py, 2- , CF , C F ; n=1,2
				3		2	5

0 1 1 -

(86) 1 1 1,

BF3·Et2O . 5 1

93-98%, (6- 50% de) [59].

Ph		O		O	BF3. Et2O (0.12.) Ph			O		O R1
		O		O				O	P NHR2
			P						P NHR2
				H + R1CH=NR2		CH2Cl2 ,				Ph
				Ph		CH2Cl2 ,
	Ph N					1.1.	Ph	N
	Ph N					1.1.	Ph	N	H
			H						H
	86

R1= Ph,2- , i-Pr, Ph; R2= Bn, t-Bu, CH2COOEt

$1 (87), in situ N- -2-1-

(88), 1- , -

CuI , c 1

1 2 1 1 1-

1 (88) [60].

N R

R1MgCl

MgCl

R2Br

R4(R3O)PHO

(R3O)2P

NHR

CuI-

R=Bn, c -Hex, CHMePh;

R = Et, t -Bu, Bn, c-Hex, allyl ;

R3= Bn, allyl,4

-MeOC H CH , MeC

C-CH , 4

-BrC H CH , R4=R3O, Ph

2 N-1 1 -

%: ,

, 1, , 1 [61-63]. * 1 1 40-450,, 1, 1 -

1 . + 2 -

36 , 2-8 -

1,5 1. 4

2 1 1. + 1 (89)

69-99%.

R1 R2													O
				CdI2, C6H6						R1
													P(OEt)		2
	+ HP(O)(OEt) 2

						0
						0
N			40-45				C			2			3
3										2			3
3									R					NHR
	R								R					NHR
	R
											89
89, R1=H, R2=Pr, R3=t-Bu (a); R1=H, R2=i-Pr,
R3=t-Bu ( ); R1=H, R2=Et, R3=cyclo-C H										11	( );
								6		11
R1=H, R2=Ph, R3=Me ( ); R 1=H,R2=Ph,
R3=Ph ( ); R1=H, R2=cyclo -C H						, R3=cyclo -C H						11	( );
			6		11						6	11
R1=R2=cyclo -C H		11	, R3=cyclo-C H				11	( );
6		11			6		11

R1=H, R2=3-Py, R3=Ph ( ); R 1=H, R2=Ph, R3=CHPh2 ( ).

*-2 . +

69-78%, – 52%.

R2			O
				PPhR1
	H	CdI2, C6H6 R2

HP(O)PhR1+
		o

N	R3	40-45 C	NHR3

		90

90, R1=EtO, R2=i-Bu, R3=t-Bu (a); R1EtO,

R2=R3=Ph ( ); R1=Ph, R2=i-Bu, R3=t-Bu ( )

% – BF3•Et2O, ZnCI2, LiCIO4, LiOTf, Sc(OTf)3 Yb(OTf)3 – 1 α-1 1 3-

(91) 1 1 [64].

OEt

Yb(OTf)3 Ts

OEt

N P

NHPh

PhCH=N

NHPh

CH2Cl2,

Bn Ph

) 2 1 : -

96%, 1 92 :92 – 97:3 90:10,

R1=1- , R2=Ph R1=2- , R2=Ph, . , 1 (R)-BINOL 1 3 1

1 1 1 -

1 LnMB (M=Li, K, Na),

% [65]. ) 1

1 1 1 , 2-

3 1 [66].

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