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Российский химико-технологический университет им. Д.И. Менделеева

Предмет:

Методы современного органического синтеза

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МСОС Лекции с поиском и закладками

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<<< < Предыдущая 1 2 3 4 5 6 7 8 9 10 11 12 13 1415 / 1915 16 17 18 19 > Следующая >>>

3. CMHTe3bl Ha ocHose MOC

3.6. MOC KaK HYKlleOq>H/lbl e peaK4MRX 3aMeW,eHMff

• AnR MOC a/lKH/lbHOfO THna peaKU,HH HyKJ1eo4>MJ1bHOfO 3aMeU\eHHR He xapaKTepHbl

AnKeH

R'-Hal

Alk -R'

•

Xi_,

-HHal Alk-M

Alk-H: pKa=S0-60

• MOC 6eH3H/lbHblMH, a1111HJ1bHblMH, apHllbHblMH M allKHHH/lbHblMM paAHKa/laMM

MOryT ecrynaTb B peaKU,HM HyK11eo4>HJ1bHOfO 3aMeU\eHMR

R'-Hal

r-tt

Bn-H

AII-H

R-M

R -R'

SN2

013-9

pKa

R-H: pKa=36-10

5 -

Bn-Li

sn-{,

-LiBr SN2

,,H 58%

hcheko

•MeH..

Mg8r Br Ot-Bu

84%

MeMgBr

\ o

- .

Ot -Bu

3. CHHTe3bl Ha ocHose MOC

3.6. MOC KaK HyKJ1eo4>M11b1 B peaK4&.1RX 3aMe1.14eHMR
,	Buli ..	Br CI			Cl AmS02TyrOH
N/4	THF/-78°C			N::-..	NaOH
			SN2

..ll

0 :::::,...

	0	HN
		..
		H2/Pt02
	0 H
HN
	11
,
	/s.
o"

	I	0
		0
		0
		0
	:::::,...	HN, I/
0	:::::,...	HN, I/
		s
		o"l.
Tl'lpocj:)1'!6aH		o"l.

					r-\
				MgBr O		/2

Br			THF/RT				91°/o
			THF/RT	:::::,...
				:::::,...
							1.2. SnN l
	I	I
	Bu--fN		11
	HN OH						NaOH
							3. Tr-CI/NEt3
	NaOMe/DMF						3. Tr-CI/NEt3
	NaOMe/DMF			83%			4. HCI

I I

:::::,...

			Bu
	I	N
		NN
......,/:::::,...		(	}Cl-
:::::,...	JloJapTaH OH		65%

3. CHHTe3bl Ha ocHoee MOC

3.7. PeaK4111111 MOC c a., -HeHaCblLJ.4eHHblMIII COeAIIIHeHMffMIII

		+	R'	R R"		H .. R'
				OM	(±)
		0
6 -	R'	R"		R OM
R-M				R OM		H(±)	R
			R' R"			H(±)	R'
			R' R"				R'

R	R"

• MOC c a,l3-HeHacb1W,eHHblMH a/lbAerHAaMH AalOT npOAYKTbl 1,2-Ad

0	1. Me-MgBr
	1. Me-MgBr

	H 2. NH4CI

86%

• llHTHHOC c a,j3-HeHaCblW,eHHblMH KeroHaMH raK>Ke Aa10r npOAYKTbl 1,2-Ad

1.t-Bu-Li

2.NH4CI

t;i

75%

3. CHHTe3bl Ha ocHoee MOC

3.7. PeaK4MM MOC c a,f3-HeHaCbll1,\eHHblMM COeAMHeHMRMM

•MarHHM-OC c a,!3-HeHacbtlJ.\eHHbtMH KeroHaMH Aa10r cMecb npOAYKTOB 1,2- H 1,4-Ad. BBeAeHHe A06aeoK 00380/lffeT perHoceneKTHBHO npoBOAHTb Ad C HeHaCbtlJ.\eHHblMH KeTOHaMH

•CeCl3 Kara111113111pyer Ad no Kap60HHJ1bHbtM rpynnaM (AJ'lff eH0111113y101J.\HXCJ1 KeroHoe)

OLi

Bu-Li	1. Bu-Li/CeCl3		©0
•			)=,Q-CeCl3 141114 Bu-CeCl2
•		2. NH4CI	)=,Q-CeCl3 141114 Bu-CeCl2
-BuH		2. NH4CI
-BuH

• CeCl3 Kara11H3111pyer 1,2-Ad AJ'lff a.,!3-HeHaCbllJ.\eHHblXKeroHoe

0	1. Me-MgBr/CeCl3/THF		OH
	1. Me-MgBr/CeCl3/THF		80%

		2. NH4CI
		2. NH4CI

• cu+1 (Cul, Li2CuCl4 ) Kara111113111pyer 1,4-Ad AJ'lff a.,j3-HeHaCbtlJ.\eHHbtXKero1-1oe

0 1. Me-MgBr/Cul/THF 0

2. NH4CI

77%

hchel<otikhin

• MeAbOpraHH"leCKHe COeAHHeHHJI JIB/IAIOTCA HHTepMeAHaTaMH peaK4HH YllbMaHa B CHHTe3e CHMMeTpH"IHblX 6111ap111110B

Cu •		Ph-I
IT
-Cul	/J>--Cu	-Cul
-Cul	/J>--Cu	-Cul

80%

• 6011ee 34>4>eKTHBHO A/IA 4>opMMpOBaHHA C-C CBA3eM np111MeHeH111e KynpaTOB r11111MaHa (HopMaH-Kop111), OAHaKO OHH HeCTa6H/lbHbl, oco6eHHO R= 2° Ill 3°

	Cul	0		] Li	©
R-Li		• I R-Cu-	R	] Li
R-Li	THF -Lil		R

• aCTO 6011ee YA06HO MCnO/lb30BaTb HeCHMMeTpH"IHble KynpaTbl (R=CN, a4eTe/leHHA) - t<ynpaTbl C «HenepeHOCMMblMH» OCTaTt<aMH:

R-Li

CuCN

[

]

Meo

THF•

R-Cu-CN

1.Buli

Meli

Meo

2.cur

-----•►,

--)r--==--Cu- ] Li

• AHa/lorH"IHO o6pa3ylOTCA MarHe3HO-KynpaTbl

[

] 0

hchekotikhin

R-MgBr

Cul

THFJIii

R-Cu-R

MgBr

4. CHHTe3bl Ha OCHOBe KynpaTOB

KynpaTbl aKTHBHO pearHpytoT C pa3nH HblMH 3neKTpo<f>HnaMH

PRA peaK4HOHHOM cnoco6HOCTH 3neKTpo4>Hnoe

> \J >

R-OTs

R-1

R-Br

R_//

bR'

4.1. Co eTaHHe KynpaTOB c T03H/1aTaMH, OKCHpaHaMH, ranoreHonpOH3BOAHblMH

R'-x

<±>

Het

[ R- e-R]

R-Cu-R

R, R'=Alk, Vi, Ar,

[

I 0

]

R'-R

>'c

-RCu, LiX

O OEt

Xo---'"--oet

_1._L_iA_	O
_1._L_iA_
4-IIJI,	X
H ►
2.Ts-CI/Py	o__
		...,.
			--
[[>--cu-<]JLi			--
[[>--cu-<]JLi
e		<±>

OTs

... Ph

THF

Cl	Br- -	- - - Cl
	Br- -	THF

• 0AHH 1113 paAHKanos KynpaTOB He Y'-faCTByeT B peaK4HH, n03TOMY AJlff cno>KHblX

paAHKanos npHMeHfflOT KynpaTbl C «HenepeHOCHMblMH» OCTaTKaMH:
	OTHP		Me	O					1/	Br
		[			0			]	_s	_,..


THF	.		+-		Cu		OTHP			_
						..,___..J			THF, -78°C

0TH

4. CHHTe3bl Ha OCHOBe KynpaTOB

4.1. PeaKl,\HH CO\feTaHHR KynpaTOB

• Co eTaHHe C BHHHJ1ra11oreHHAaMH npoTeKaeT CTepeoceneKTHBHO C coxpaHeHHeM CTepeOXHMHH

			C			Ph2CuLi
Ph	Br	Ph2 uLi Ph		Ph	Ph	---11•►	Ph
			THF •	'-=I 99%
'-=I					Br	THF	98% Ph

• PeaKL\HR KynpaTOB C 3nOKCHAaMH npoTeKaeT 6011ee perHoceneKTHBHO, eM C APYfHMH

MOC; aHanorH HO pearHpytoT OKCeTaHbl H naKTOHbl	0

		BuMgCI
Me2Cul•i h	Q			OH
Me2Cul•i h			90%
THF HO
	o	o i
		©		OH
		2.H		OH
		2.H
		0	76%

• B peaK4Hto MO>KHO BBOAHTb 3/leKTPO<l>HJlbl C fHAPOKCH- H C/1. 3<l>HpHblMH rpynnaMH I}

•		I	•	OH
•
OH 1. LiAIH	4
	4

THF

4. CMHTe3bl Ha OCHOBe KynpaTOB

4.1. PeaKL\MM co eTaHMR KynpaTOB

• B PRAe c11yl.faes col.feTaHMe MO>KHO npoBOAMTb s KaTa/lMTMl.fecKoMeapHaHTe (Cul, Li2CuCl4)

		1/			MgCI			Cl
		1/			MgCI	---------►
		0	,,,--.;1				Li2CuCl4 (0.35%)
							Li2CuCl4 (0.35%)
						THF, o°C6 Smin
	Ph 1	.						1.PhMgCI		Ph
	Ph 1	.						1.PhMgCI
	PhMgCI/Cul (10%)							0
	OH	2. H		©				0	3%	OH
		2. H		©						OH
82%
82%

4.2. PeaK4MM c a,f3-HeHaCblL14eHHblMM KeTOHaMM

• KynpaTbl A3IOT npOAVKTbl 1,4-Ad, peaKU,HR npoTeKaeT, \fepe3 o6pa3oeaHMe eHO/lRTa, KOTOpblH MO>KHO BBOAHTb B peaKU,HM aJ1KHJ1HposaHHR/au,H11MpoeaHHR

0		Oli	0	0	0
0

	Mel	8 -	..Me2Culi		1. Me2Culi
					1. Me2Culi

					2.H©

4. Ca.-tHTe3bl Ha OCHOBe KynpaTOB

4.2. PeaKU."11A c a.,'3-HeHaCblll.\eHHblMl,1 KeTOHaM"1

0		1.
•	I	2.
•

TBDPSO

[	Me			0	Am	@
	Me
	_o		Cu		OTBDPS l Li
		_--==--	Cu		OTBDPS l Li		0,
			_r(				0,
			_r(				----.i'"
		)

0 MeO

TBDPscf•

::::::::..__/.........,_/o "'

►

Pd/CaC03/PbO

OTBDPS

...	0	-	OMe	1. TBAF/MeCN	0	-	OMe
...	$	OTBDPS	OMe		0
	$
	"'
TBDPSO						OH	PGE2 (A11HonpocroH)

5. CTepeoxMMMff np1>1coeAMHeHMff MOC no C=O rp.

npMCOeAMHeHMe MOCK aJ1bAer111AaM C XHpallbHblM L\eHTpOM a.-nono>KeHHH npoTeKaeT AH3CTepeoceneKTHBHO

1. Buli

CTepeoxHMH4eCKHH pe3y11bTaT Ad npeACKa3blBaeTCR npae11110M KpaMa: e npeAn04THTe/1bHOH KOH<PopMau,1111 C=O rpynna pacnonaraeTCR Me>KAY RM H R5, a Nu npHCOeAHHReTCR co CTOPOHbl HaHMeHbWHX crepH4eCKHX npenRTCTBHH.

H/1H npaBH/lOM CS>e/1KIIIH3-AHHa: 3T3K3 HyK11eocp11111a no Kap60HM/1bHOH rpynne npOMCXOAHT co CTOpOHbl, npoTHBOn0/10>KHOH HaM6011ee o6beMHOMY 33MeCT11tTeJ1t0, npH4eM caMa aTaKa, HanpaeneHa noA yrnoM 610pr1,1 - AYHHL\3 (107°)

	npae1,1110	npae111no
		CS>enKHHa
	KpaMa
		AHHa

R-M

hchekotikhin

<<< < Предыдущая 1 2 3 4 5 6 7 8 9 10 11 12 13 1415 / 1915 16 17 18 19 > Следующая >>>

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